Polymer modified asphalt roofing material

ABSTRACT

A shingle coating asphalt composition is provided that is produced from a paving grade asphalt. The asphalt composition comprises a paving-grade asphalt that has been modified with one or more polymer additives; and a secondary additive comprising one or more of a viscosity reducing agent, a wax, a salt of a fatty acid ester, and an amide of a fatty acid. The shingle coating asphalt coating composition is used to make a shingle. The shingle includes a substrate, the asphalt, and roofing granules.

RELATED APPLICATIONS

The present application claims the benefit of US Provisional PatentApplication Ser. No. 62/599,406, filed Dec. 15, 2017, titled “ROOFINGMATERIAL HAVING IMPROVED WEATHERABILITY AND IMPACT RESISTANCE” and USProvisional Patent Application Ser. No. 62/724,417, filed Aug. 29, 2018,titled “REINFORCED POLYMER MODIFIED ASPHALT ROOFING MATERIAL”, which areboth incorporated herein by reference in their entirety.

BACKGROUND

Asphalt-based roofing materials, such as roofing shingles, roll roofing,and commercial roofing, are installed on the roofs of buildings toprovide protection from the elements and to give the roof anaesthetically pleasing look. Typically, the roofing material isconstructed of a substrate such as a glass fiber mat or an organic felt,an asphalt coating on the substrate, and a protective and/or decorativesurface layer of granules of stone, mineral, sand or other particulatematerial is embedded in the tacky asphalt coating.

A common method for the manufacture of asphalt shingles is theproduction of a continuous sheet of asphalt material followed by ashingle cutting operation which cuts the material into individualshingles. In the production of asphalt sheet material, either a glassfiber mat or an organic felt mat is passed through a coater containinghot liquid asphalt filled with limestone to form a tacky, asphalt coatedsheet. Subsequently, the hot asphalt coated sheet is passed beneath oneor more granule applicators which discharge protective and decorativesurface granules onto portions of the asphalt sheet material.

In certain types of shingles, it is especially desired that the shinglesdefine a sufficiently wide area, often known in the industry as the“nail zone,” in order to make installation of roofs using shingles, suchas laminated shingles, more efficient and secure. One or more lines orother indicia painted or otherwise marked longitudinally on the surfaceof the shingle may define such a nail zone. It is especially desiredthat the shingles define a nail zone that guides installers in theplacement of nails.

Additionally, shingles may experience lift in high wind situations. Thislift may be exacerbated if the shingle tabs are not sealed or adhered tothe shingle below. Therefore, there is also a need for shingles thathave a sufficiently high nail pull-through value so that the installedshingles have improved performance in high wind situations.

Historically, coating asphalt for roofing shingles has been produced bychoosing a special grade of asphalt as the feedstock to the air blowingprocess in order to meet these properties. These special grades ofasphalt were often materials that were softer (higher penetration, lowerviscosity) than paving grade asphalt and were often called “roofer'sflux”. Unfortunately, these special grades of asphalts that can beair-blown to make coating asphalts are increasingly in short supply andtherefore can be costly compared to many other types of asphalts,particularly commodity paving asphalts.

SUMMARY

A shingle coating asphalt composition is provided that is produced froma paving grade asphalt. The asphalt composition comprises a paving-gradeasphalt that has been modified with one or more polymer additives; and asecondary additive comprising one or more of a viscosity reducing agent,a wax, a salt of a fatty acid ester, and an amide of a fatty acid. Theshingle coating asphalt coating composition is used to make a shingle.The shingle includes a substrate, the asphalt, and roofing granules.

BRIEF DESCRIPTION OF THE DRAWINGS

Exemplary embodiments of the disclosure will be apparent from the moreparticular description of certain example embodiments provided below andas illustrated in the accompanying drawings.

FIG. 1 is a schematic elevational view of an apparatus for manufacturingshingles;

FIG. 2 is a perspective view of a first embodiment of a laminatedshingle having reinforcement material;

FIG. 3 is a plan view of the front of the laminated shingle illustratedin FIG. 2;

FIG. 4 is a plan view of the back of the laminated shingle illustratedin FIGS. 2 and 3;

FIG. 5 is a perspective view of a portion of a second embodiment of alaminated shingle having reinforcement material;

FIG. 6 is an enlarged schematic elevational view of a portion of thelaminated shingle illustrated in FIGS. 2, 3, and 4;

FIG. 7 is a schematic elevational view of a spool of reinforcement;

FIG. 8 graphically illustrates the reduction in viscosity of the polymermodified asphalt coating compositions, compared to conventional asphaltcompositions;

FIG. 9 illustrates an aluminum panel coated with a conventional oxidizedpolymer modified asphalt composition, after being exposed to acceleratedweathering caused by UV lighting and controlled conditions of humidity,moisture, and temperature;

FIG. 10 illustrates an aluminum panel coated with a non-oxidized polymermodified asphalt composition that includes a secondary additive inaccordance with the present inventive concepts, after being exposed toaccelerated weathering caused by UV lighting and controlled conditionsof humidity, moisture, and temperature;

FIG. 11 illustrates two aluminum panels coated with a non-oxidizedpolymer modified asphalt composition without a secondary additive, afterbeing exposed to accelerated weathering caused by UV lighting andcontrolled conditions of humidity, moisture, and temperature;

FIG. 12 illustrates two aluminum panels coated with a non-oxidizedpolymer modified asphalt composition with a polyethylene wax additive,after being exposed to accelerated weathering caused by UV lighting andcontrolled conditions of humidity, moisture, and temperature;

FIGS. 13 and 14 schematically illustrate a test of longitudinal adhesionof a nail zone reinforcement material to a shingle;

FIG. 15 schematically illustrates a test of transverse adhesion of anail zone reinforcement material to a shingle; and

FIGS. 16 and 17 schematically illustrate a cutting test through shinglematerial (one or two layers) and nail zone reinforcement material on theshingle material;

DETAILED DESCRIPTION

The present invention will now be described with occasional reference tothe illustrated embodiments of the invention. This invention may,however, be embodied in different forms and should not be construed aslimited to the embodiments set forth herein, nor in any order ofpreference. Rather, these embodiments are provided so that thisdisclosure will be more thorough, and will convey the scope of theinvention to those skilled in the art.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. The terminology used in thedescription of the invention herein is for describing particularembodiments only and is not intended to be limiting of the invention. Asused in the description of the invention and the appended claims, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth as used in the specification and claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless otherwise indicated, the numerical properties setforth in the specification and claims are approximations that may varydepending on the desired properties sought to be obtained in embodimentsof the present invention. Notwithstanding that the numerical ranges andparameters setting forth the broad scope of the invention areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical values, however,inherently contain certain errors necessarily resulting from error foundin their respective measurements.

As used in the description of the invention and the appended claims, theterm “longitudinal” or “longitudinally” is defined as substantiallyparallel with the machine direction.

As used in the description of the invention and the appended claims, theterms “shingle blow off” or “blow off” are defined as the occurrence ofinstalled shingles being forced off a roof deck when the installedshingles are subjected to high winds. Also, the term “shingle blowthrough” or “blow through” are defined as the situation that occurs whena nail has been driven too deeply into the shingle and the nail headpenetrates through at least the shingle overlay.

As used in the description of the invention and the appended claims, theterm “wet” or “wet out” is defined as the ability of sealant or adhesiveto flow and/or reflow over a surface to maximize bond strength based ona larger contact area.

As used in the description of the invention and the appended claims, theterm “waywind” is defined as fibers, or strips of material or fabricthat are collected, applied to, or wound on a spool or bobbin in apattern that changes the angle of the material relative to thelongitudinal axis of the spool.

Composite shingles, such as asphalt shingles, are a commonly usedroofing product. One example of a composite shingle is disclosed in U.S.Pat. No. RE46,177, which is incorporated herein by reference in itsentirety. Asphalt shingle production generally includes feeding a basematerial from an upstream roll and coating it first with a roofingasphalt material, then a layer of granules. The base material istypically made from a fiberglass mat provided in a continuous shinglemembrane or sheet. It should be understood that the base material may beany suitable support material.

Composite shingles may have a headlap region and a prime region. Theheadlap region may be ultimately covered by adjacent shingles wheninstalled upon a roof. The prime region will be ultimately visible whenthe shingles are installed upon a roof.

The granules deposited on the composite material shield the roofingasphalt material from direct sunlight, offer resistance to fire, andprovide texture and color to the shingle. The granules generally involveat least two different types of granules. Headlap granules are appliedto the headlap region. Headlap granules are relatively low in cost andprimarily serve the functional purposes of covering the underlyingasphalt material for a consistent shingle construction, balancing sheetweight, and preventing overlapping shingles from sticking to oneanother. Colored granules or other prime granules are relativelyexpensive and are applied to the shingle at the prime regions. Primegranules are disposed upon the asphalt strip for both the functionalpurpose of protecting the underlying asphalt strip and for providing anaesthetically pleasing appearance of the roof

The performance of an installed shingle, such as in high windconditions, may be enhanced by reinforcing the nail zone of the shingle.By reinforcing the nail zone, the occurrence of nail blow through duringshingle installation may be reduced. Reducing the occurrence of nailblow through advantageously reduces the possibility of a roof leak ifwater travels under the shingle tab. A reinforced nail zone alsoimproves the efficiency of the shingle installer by reducing thelikelihood of nail blow through when the shingle is weakened due to hightemperatures, such as when the roof or shingle temperature is aboveabout 120 degrees F., or when nail gun air pressure is too high. Thereinforced nail zone may also provide a defined and relatively wide areain which the installer may nail. Advantageously, the reinforced nailzone will increase the force required to pull a nail through theshingle, thereby reducing the likelihood of shingle blow off.

The nail zone may also be used as the bonding substrate area or bondingsurface for tab sealant bonded to the underside of the tabs of theoverlay sheet. The nail zone may provide an improved bonding surface fortab sealant.

It is known that most debonding energy, such as is generated between thetab sealant and the bonding surface is due to viscoelastic loss in thetab sealant as it is stretched during debonding. Further, the polymermodified asphalt sealants typically used as tab sealants on shingles maylose their viscoelastic characteristics when the temperature drops to 40degrees F. or below.

Advantageously, the use of woven or non-woven fabric to reinforce thenail zone and to define the bonding surface for tab sealant has beenshown to improve or retain debonding loads of polymer modified asphaltsealants relative to shingles without a reinforced nail zone atrelatively low temperatures, such as temperatures below about 40 degreesF. This relatively strong debonding load between woven or non-wovenfabric and modified asphalt sealants, including polymer and non-polymermodified asphalt tab sealants, occurs because the woven or non-wovenfabric mechanically bonds to the sealant. For example, mechanicalattachment occurs as the polymer modified asphalt sealant flows aroundindividual filaments and fiber bundles within the woven or non-wovenfabric during bonding. The energy required to debond the polymermodified asphalt sealant from the woven or non-woven fabric is increasedor comparable to the energy required to debond the polymer modifiedasphalt sealant from a shingle without a reinforced nail zone. Becausethe tab sealant is reinforced with the filaments and fiber bundleswithin the woven or non-woven fabric at the interface between thepolymer modified asphalt sealant and the woven or non-woven fabric, theinterior of the sealant becomes the weakest portion of the bond.

An additional advantage of using woven or non-woven fabric to reinforcethe nail zone is that the fabric may be installed during shingleproduction. During shingle production, the woven or non-woven fabric maybe pushed into the hot, filled-asphalt coating, such that some of thefilled-asphalt bleeds up and around the individual fibers and fiberbundles of the fabric. This creates a positive mechanical bond betweenthe fabric and the shingle substrate. Further, the filled-asphalt thatbleeds up and into the fabric aids in forming a bond between the tabsealant and the shingle because the filled-asphalt diffuses into the tabsealant. When installed on a roof, this creates a robust continuous pathfor the transfer of debonding loads from the tab above to the nail inthe shingle below.

Referring now to the drawings, there is shown in FIG. 1 an apparatus 10for manufacturing an asphalt-based roofing material according to theinvention. The illustrated manufacturing process involves passing acontinuous sheet of substrate or shingle mat 11 in a machine direction12 through a series of manufacturing operations. The mat 11 usuallymoves at a speed of at least about 200 feet/minute (61 meters/minute),and typically at a speed within the range of between about 450feet/minute (137 meters/minute) and about 800 feet/minute (244meters/minute). The sheet, however, may move at any desired speed.

In a first step of the manufacturing process, the continuous sheet ofshingle mat 11 is payed out from a roll 13. The shingle mat 11 may beany type known for use in reinforcing asphalt-based roofing materials,such as a nonwoven web of glass fibers. Alternatively, the substrate maybe a scrim or felt of fibrous materials such as mineral fibers,cellulose fibers, rag fibers, mixtures of mineral and synthetic fibers,or the like.

The sheet of shingle mat 11 is passed from the roll 13 through anaccumulator 14. The accumulator 14 allows time for splicing one roll 13of substrate to another, during which time the shingle mat 11 within theaccumulator 14 is fed to the manufacturing process so that the splicingdoes not interrupt manufacturing.

Next, the shingle mat 11 is passed through a coater 16 where a coatingof asphalt 17 is applied to the shingle mat 11 to form a firstasphalt-coated sheet 18. The asphalt coating 17 may be applied in anysuitable manner. In the illustrated embodiment, the shingle mat 11contacts a supply of hot, melted asphalt 17 to completely cover theshingle mat 11 with a tacky coating of asphalt 17. However, in otherembodiments, the asphalt coating 17 could be sprayed on, rolled on, orapplied to the shingle mat 11 by other means. Typically, the asphaltcoating is highly filled with a ground mineral filler material,amounting to at least about 60 percent by weight of the asphalt/fillercombination. In one embodiment, the asphalt coating 17 is in a rangefrom about 350.degree. F. to about 400.degree. F. In another embodiment,the asphalt coating 17 may be more than 400.degree. F. or less than350.degree. F. The shingle mat 11 exits the coater 16 as a firstasphalt-coated sheet 18. The asphalt coating 17 on the firstasphalt-coated sheet 18 remains hot.

A continuous strip of a reinforcement material 19, as will be describedin detail herein, may then be payed out from a roll 20. Thereinforcement material 19 adheres to the first asphalt-coated sheet 18to define a second asphalt-coated sheet 22. In a first embodiment, thereinforcement material 19 is attached to the sheet 18 by the adhesivemixture of the asphalt in the first asphalt-coated sheet 18. Thereinforcement material 19, however, may be attached to the sheet 18 byany suitable means, such as other adhesives. As described in detailbelow, the material 19 may be formed from any material for reinforcingand strengthening the nail zone of a shingle, such as, for example,paper, film, scrim material, and woven or non-woven glass fibers.

The resulting second asphalt coated sheet 22 may then be passed beneatha series of granule dispensers 24 for the application of granules to theupper surface of the second asphalt-coated sheet 22. The granuledispensers may be of any type suitable for depositing granules onto theasphalt-coated sheet. A granule dispenser that may be used is a granulevalve of the type disclosed in U.S. Pat. No. 6,610,147 to Aschenbeck.The initial granule blender 26 may deposit partial blend drops ofbackground granules of a first color blend on the tab portion of thesecond asphalt coated sheet 22 in a pattern that sets or establishes thetrailing edge of subsequent blend drops of a second color blend (of anaccent color) and a third color blend (of a different accent color). Forpurposes of this patent application, the first color blend and thebackground granules are synonymous. The use of initially applied partialblend drops to define the trailing edge of subsequent blend drops isuseful where accurate or sharp leading edges are possible, but accuratetrailing edges at high shingle manufacturing speeds are difficult.

As is well known in the art, blend drops applied to the asphalt-coatedsheet are often made up of granules of several different colors. Forexample, one particular blend drop that is supposed to simulate aweathered wood appearance might actually consist of some brown granules,some dark gray granules, and some light gray granules. When thesegranules are mixed together and applied to the sheet in a generallyuniformly mixed manner, the overall appearance of weathered wood isachieved. For this reason, the blend drops are referred to as having acolor blend, which gives an overall color appearance. This overallappearance may be different from any of the actual colors of thegranules in the color blend. In addition, blend drops of darker andlighter shades of the same color, such as, for example, dark gray andlight gray, are referred to as different color blends rather than merelydifferent shades of one color.

As shown in FIG. 1, the series of dispensers 24 includes fourcolor-blend blenders 26, 28, 30, and 32. Any desired number of blenders,however, may be used. The final blender may be the background blender34. Each of the blenders may be supplied with granules from sources ofgranules, not shown. After the blend drops are deposited on the secondasphalt-coated sheet 22, the remaining, uncovered areas are still tackywith warm, uncovered asphalt, and the background granules from thebackground blender 34 will adhere to the areas that are not alreadycovered with blend drop granules. After all the granules are depositedon the second asphalt-coated sheet 22 by the series of dispensers 24,the sheet 22 becomes a granule-covered sheet 40.

In the illustrated embodiment, the reinforcement material 19 includes anupper surface to which granules substantially will not adhere. Granulesmay therefore be deposited onto substantially the entire secondasphalt-coated sheet 22, including the material 19, but wherein thereinforcement material 19 includes an upper surface to which granulessubstantially will not adhere.

The granule-covered sheet 40 may then be turned around a slate drum 44to press the granules into the asphalt coating and to temporarily invertthe sheet so that the excess granules will fall off and will berecovered and reused. Typically, the granules applied by the backgroundblender 34 are made up by collecting the backfall granules falling fromthe slate drum 44.

The granule-covered sheet 40 may subsequently be fed through a rotarypattern cutter 52, which includes a bladed cutting cylinder 54 and abackup roll 56, as shown in FIG. 1. If desired, the pattern cutter 52may cut a series of cutouts in the tab portion of the granule-coveredsheet 40, and cut a series of notches in the underlay portion of thegranule-covered sheet 40.

The pattern cutter 52 may also cut the granule-covered sheet 40 into acontinuous underlay sheet 66 and a continuous overlay sheet 68. Theunderlay sheet 66 may be directed to be aligned beneath the overlaysheet 68, and the two sheets may be laminated together to form acontinuous laminated sheet 70. As shown in FIG. 1, the continuousunderlay sheet 66 may be routed on a longer path than the path of thecontinuous overlay sheet 68. Further downstream, the continuouslaminated sheet 70 may be passed into contact with a rotary lengthcutter 72 that cuts the laminated sheet into individual laminatedshingles 74.

In order to facilitate synchronization of the cutting and laminatingsteps, various sensors and controls may be employed. For example,sensors, such as photo eyes 86 and 88 may be used to synchronize thecontinuous underlay sheet 66 with the continuous overlay sheet 68.Sensors 90 may also be used to synchronize the notches and cutouts ofthe continuous laminated sheet with the end cutter or length cutter 72.

In a second embodiment, the reinforcement material may be attached to alower surface (the downwardly facing surface when viewing FIG. 1) of themat 11, the first asphalt coated sheet 18, the second asphalt coatedsheet 22, or the granule-covered sheet 40, as shown at 19A and 19B inFIG. 1. The reinforcement material 19A and 19B may be attached to themat 11, the first asphalt coated sheet 18, the second asphalt coatedsheet 22, or the granule-covered sheet 40 by any suitable means, such ashot, melted asphalt, other adhesives, or suitable fasteners. In such anembodiment, the reinforcement material 19A and 19B may be attached tothe lower surface of the nail zone of either of the overlay sheet 68 orthe underlay sheet 66, thereby reinforcing and strengthening the nailzone as described herein.

Referring now to FIGS. 2, 3, and 4, a first embodiment of a laminatedroofing shingle is shown generally at 74. In the illustrated embodiment,the shingle 74 has a length L and includes the overlay sheet 68 attachedto the underlay sheet 66 and has a first end or leading edge 74C and asecond end or trailing edge 74D. In the illustrated embodiment, thelaminated roofing shingle 74 has a length L of about 39.375 inches.Alternatively, the length L may be within the range of from about 39.125inches to about 39.625 inches. The shingle 74 may also be manufacturedhaving any other desired length. The shingle 74 also includes alongitudinal axis A. The overlay sheet 68 may include a headlap portion76 and a tab portion 78. The headlap portion 76 may include a lower zone76A and an upper zone 76B. The tab portion 78 defines a plurality oftabs 80 and cutouts 82 between adjacent tabs 80.

In the illustrated embodiment, the tab portion 78 includes four tabs 80,although any suitable number of tabs 80 may be provided. The headlapportion 76 and the tabs 80 may include one or more granule patternsthereon. Each cutout 82 has a first height H1. In the illustratedembodiment, the cutout 82 has a first height H1 of about 5.625 inches.Alternatively, the first height H1 may be within the range of from about5.5 inches to about 5.75 inches. In the illustrated embodiment, thecutouts 82 are shown as having the same height H1. It will be understoodhowever, that each cutout 82 may be of different heights. A line B iscollinear with an upper edge 82A of the cutouts 82 and defines an upperlimit of an exposed region 84 of the underlay sheet 66. In theillustrated embodiment, the height of the exposed region 84 is equal tothe first height H1, although the height of the exposed region 84 may beany desired height. In a shingle wherein the cutouts 82 have differentheights, the line B may be collinear with an upper edge 82A of thecutout 82 having the largest height. In the illustrated embodiment, theoverlay sheet 68 has a second height H2.

The reinforcement material 19 has a width W of about 1.0 inch.Alternatively, the width W may be within the range of from about 0.75inch to about 1.5 inches. Additionally, the width W may be within therange of from about 0.5 inch to about 2.0 inches. The reinforcementmaterial 19 may be disposed longitudinally on the headlap portion 76. Inthe illustrated embodiment, the reinforcement material 19 extendslongitudinally from the first end 74A to the second end 74B of theshingle 74 within the lower zone 76A of the headlap portion 76. A loweredge 19A of the reinforcement material 19 may be spaced apart from theline B by a distance D1. In the illustrated embodiment, the distance D1is about 0.25 inch. Alternatively, the distance D1 may be within therange of from about 0.125 inch to about 0.375 inch. The distance D1 mayhowever, be of any other desired length. For example, if desired, thereinforcement material 19 may substantially cover the entire headlapportion 76 of the overlay sheet 68. It will be understood that thereinforcement material 19 need not extend from the first end 74A to thesecond end 74B of the shingle 74, and may be disposed in one or moresections or portions on the shingle 74.

The reinforcement material 19 defines a reinforced nail zone 98 and mayinclude text such as “NAIL HERE”, as shown in FIG. 2. It will beunderstood, however, that any other text or other indicia may beincluded on the reinforcement material 19. It will also be understoodthat the reinforcement material 19 can be provided without such text orindicia. These indicia on the reinforcement material 19 ensure that thereinforced nail zone 98 may be easily and quickly identified by theshingle installer.

In the embodiment illustrated in FIGS. 2 and 4, the underlay sheet 66includes a leading edge 66A and a trailing edge 66B and has a thirdheight H3. In the illustrated embodiment, the height H3 of the underlaysheet 66 is about 6.625 inches. Alternatively, the height H3 may bewithin the range of from about 6.5 inches to about 6.75 inches. Theunderlay sheet 66 may also be manufactured having any other desiredheight.

In the illustrated embodiment, the third height H3 of the underlay sheet66 is equal to about one-half the second height H2 of the overlay sheet68. The overlay sheet 68 and the underlay sheet 66 thereby overlap todefine a two-layer portion of the laminated shingle 74 and asingle-layer portion of the laminated shingle 74. More specifically, aregion of the underlay sheet 66 overlaps a region of the headlap portion76 of the overlay sheet 68, thereby defining a two-layer portion and asingle-layer portion of the laminated shingle 74 within the headlapportion 76. At least a portion of the reinforcement material 19 isadhered to the single-layer portion of the laminated shingle 74.Alternately, the third height H3 of the underlay sheet 66 may be greaterthan one-half of the second height H2 of the overlay sheet 68. Thisrelationship between the underlay sheet 66 and the overlay sheet 68allows the reinforcement material 19 to be positioned such that areinforced nail zone is provided at the two-layer portion of thelaminated shingle 74.

Referring now to FIG. 4, a back side of the laminated shingle 74 isshown. If desired, a continuous strip of release tape 94 may extendlongitudinally and may be adhered to an upper surface of the back sideof the laminated shingle 74 adjacent and parallel to a trailing edge 74Dof the laminated shingle 74. The release tape 94 is positioned such thatit will be opposite the tab sealant 96 when the laminated shingles 74are stacked, such as when packaged for shipment. The release tape 94 maybe spaced a distance D1 from the trailing edge 74D of the laminatedshingle 74. In the illustrated embodiment, the release tape 94 is spacedabout 0.125 inches from the trailing edge 74D of the laminated shingle74. Alternatively, the release tape 94 may be placed at any desiredlocation on the back side of the laminated shingle 74, such that therelease tape 94 contacts and covers the sealant 96 when a plurality ofthe laminated shingles 74 are stacked in a bundle, such as for shipping.

A discontinuous bead of tab sealant 96 may extend longitudinally and maybe adhered to a lower surface of the back side of the laminated shingle74 adjacent and parallel to a leading edge 74C of the laminated shingle74. The tab sealant 96 may be spaced a distance D2 from the leading edge74C of the laminated shingle 74. In the illustrated embodiment, the tabsealant 96 is spaced about 0.5 inches from the leading edge 74C of thelaminated shingle 74. Alternatively, the tab sealant 96 may be spacedwithin the range of from about 0.375 inch to about 0.625 inch from theleading edge 74C of the laminated shingle 74. In the illustratedembodiment, the tab sealant 96 includes segments 96S having a length 96Lof about 3.0 inches. Alternatively, the tab sealant segments 96S mayhave a length 96L within the range of from about 2.25 inches to about4.25 inches. The tab sealant segments 96S may be spaced apart a distance96D. In the illustrated embodiment, the tab sealant segments 96S arespaced about 1.0 inch apart. Alternatively, the tab sealant segments 96Smay be spaced within the range of from about 0.25 inch to about 1.5inches apart.

The tab sealant segments 96S may have a width 96W. In the illustratedembodiment, the tab sealant segments 96S have a width 96W of about 0.5inch. Alternatively, the tab sealant segments 96S may have a width 96Wwithin the range of from about 0.375 inches to about 0.675 inches. Thetab sealant segments 96S may also be applied having any other desiredwidth. In the illustrated embodiment, the tab sealant segments 96S havea thickness of about 0.035 inch. Alternatively, the tab sealant segments96S may have a thickness within the range of from about 0.028 inches toabout 0.050 inches. The tab sealant segments 96S may also be appliedhaving any other desired thickness. It will be understood that the beadof tab sealant 96 may be applied as a continuous bead of sealant.

In the illustrated embodiment, wherein the reinforcement material 19 hasa width W of about 1.0 inch, the reinforcement material 19 is positionedsuch that about 75 percent (0.75 inch) of the reinforced nail zone ispositioned over the two-layer portion of the laminated shingle 74, andabout 25 percent (0.25 inch) of the reinforced nail zone is positionedover the single-layer portion of the laminated shingle 74.Alternatively, within the range of from about 62.5 percent (0.625 inch)to about 87.5 percent (0.875) of the reinforced nail zone is positionedover the two-layer portion of the laminated shingle 74, and within therange of from about 12.5 percent (0.125 inch) to about 37.5 percent(0.375 inch) of the reinforced nail zone is positioned over thesingle-layer portion of the laminated shingle 74.

Additionally, within the range of from about 50 percent (0.50 inch) toabout 100 percent (1.0 inch) of the reinforced nail zone is positionedover the two-layer portion of the laminated shingle 74, and within therange of from about 0.0 percent (0.0 inch) to about 50 percent (0.50inch) of the reinforced nail zone is positioned over the single-layerportion of the laminated shingle 74. For example, a second embodiment ofthe laminated shingle 174 is shown in FIG. 5 and includes the underlaysheet 166 and the overlay sheet 168. The reinforcement material 19 isattached to the overlay sheet 168 as described above and is positionedsuch that about 100 percent of the reinforced nail zone 198 ispositioned over the two-layer portion of the laminated shingle 174, andabout 0 percent of the reinforced nail zone 198 is positioned over thesingle-layer portion of the laminated shingle 174.

An enlarged schematic view of a portion of the laminated shingle 74 isshown in FIG. 6. As shown, the reinforcement material 19 of thereinforced nail zone 98 is shown with a nail 90 installed through thereinforcement material 19 where it is adhered to the single-layerportion of the laminated shingle 74. The nail 90 extends only throughthe reinforcement material 19 and the overlay sheet 68, but a portion ofthe nail head 92 (left most portion of the nail head 92 when viewingFIG. 6) extends over the two-layer portion of the laminated shingle 74.Advantageously, the position of the reinforcement material 19 relativeto the two-layer portion of the laminated shingle 74 significantlyreduces the occurrence of shingle blow through and significantlyincreases nail pull through resistance during installation and winduplift events such as occurs during high winds. Even if an installerdrives a nail 90 through the upper most portion of the reinforcementmaterial 19 (right most portion of reinforcement material 19 whenviewing FIG. 6), as shown in FIG. 6, at least a portion of the nail head92 will extend over and engage the two-layer portion of the laminatedshingle 74, and thus be substantially prevented from blowing through thelaminated shingle 74.

The embodiment of the reinforcement material 19 illustrated in FIGS. 2and 3 is a woven material or web woven from polyester fabric yarns ofabout 150 denier. Alternatively, the reinforcement material 19 may be amaterial woven from fabric yarns within the range of from about 125denier to about 175 denier. Additionally, the reinforcement material 19may be a material woven from fabric yarns within the range of from about100 denier to about 200 denier.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 is a 150 denier material having a density of about 80yarns per inch in the warp or machine direction and about 45 yarns perinch in the cross-machine direction. Alternatively, the reinforcementmaterial 19 may be a woven material having a density within the range offrom about 65 yarns per inch to about 90 yarns per inch in the warpdirection and within the range of from about 35 yarns per inch to about55 yarns per inch in the cross-machine direction.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 may have a weight of about 2.8 ounces/yard.sup.2.Alternatively, the reinforcement material 19 may be a woven materialhaving a weight within the range of from about 2.0 ounces/yard.sup.2 toabout 3.5 ounces/yard. Additionally, the reinforcement material 19 maybe a woven material having a weight within the range of from about 1.5ounces/yard. sup.2 to about 4.5 ounces/yard.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 may also have a thickness of about 9.5 mils.Alternatively, the reinforcement material 19 may be a woven materialhaving a thickness within the range of from about 5 mils to about 15mils. Additionally, the reinforcement material 19 may be a wovenmaterial having a thickness within the range of from about 3 mils toabout 20 mils. The reinforcement material 19 may also have having anyother desired thickness.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 may further have an air permeability of about 210cm.sup.3/s/cm.sup.2, measured, for example, in accordance with ASTMD737. Alternatively, the reinforcement material 19 may be a wovenmaterial having an air permeability within the range of from about 160cm.sup.3/s/cm.sup.2 to about 260 cm.sup.3/s/cm.sup.2. Additionally, thereinforcement material 19 may be a woven material having an airpermeability within the range of from about 85 cm.sup.3/S/cm.sup.2 toabout 335 cm.sup.3/s/cm.sup.2.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 is formed from extruded polyester fibers that are woven.Alternatively, the woven reinforcement material 19 may be formed fromany other suitable material, such as nylon, KEVLAR.RTM., cotton, rayon,and fiberglass. It will be understood that the properties andcharacteristics, such as weight, density, and air permeability, of thepolyester reinforcement material 19 described above will vary when thereinforcement material 19 is formed from materials other than polyesterfiber. Further, polypropylene and/or other polymers may be used to formthe woven reinforcement material 19 if either the reinforcement material19 and/or the first asphalt-coated sheet 18 are cooled so that thereinforcement material 19 does not melt or shrink when it contacts thefirst asphalt-coated sheet. It will be understood that the embodimentsof the woven reinforcement material described herein may have anydesired weave pattern.

It will be understood that the reinforcement material 19 may be formedas a non-woven mat. In a first embodiment of a non-woven mat, thenon-woven mat may comprise about 10 percent glass fiber and about 90percent bi-component polymer fiber, or a glass to bi-component fiberratio of 10:90. One example of a suitable bi-component fiber is a fiberhaving a polyethylene (PE) outer sheath and a polyethylene terephthalate(PET) core, wherein the bi-component fibers have a 50:50 by weightsheath to core ratio. It has been shown that the glass fiber in thereinforcement material 19 helps to ensure dimensional stability of thereinforcement material 19 when it is cured and when it is applied to ashingle while the asphalt of the shingle is still hot.

It will be understood that non-woven mats having glass to bi-componentfiber ratios other than 10:90 may also meet or exceed the desired bondstrengths over a range of temperatures. For example, non-woven matshaving glass to bi-component fiber ratios within the range of from about5:95 to about 25:75 may also be used.

It has been shown that a non-woven mat comprising about 10 percent glassfiber and about 90 percent bi-component fiber with a 50:50 PE sheath toPET core ratio does not require a binder, as the PE of the outer sheathmelts when applied to hot asphalt during shingle production and bondsthe glass, and polymer fibers together. The embodiments of the non-wovenmats disclosed herein and comprising about 10 percent glass fiber andabout 90 percent bi-component fiber were cured in an oven having atemperature of about 350 degrees F. It will be understood that ifdesired, a coupling agent or bond promoter may be applied to the fiberswithin the non-woven mat to enhance bond strength between the glass, andpolymer fibers.

Advantageously, a non-woven mat having bi-component fiber as describedabove is sufficiently strong and will not de-laminate when installed ona roof. The non-woven mat having bi-component fiber also forms a verystrong bond with both the filled-asphalt of the shingle and the tabsealant. Further, the filled-asphalt of the shingle will not bleedthrough the embodiment of the non-woven mat described above.

In the exemplary shingle 74 illustrated in FIG. 2, the shingle 74 mayhave a nail pull-through value, measured in accordance with a desiredstandard, such as prescribed by ASTM test standard D3462. For example,the shingle 74 may have a nail pull-through value that is greater thanin an otherwise identical shingle without the reinforcement material 19.

Improved nail pull-through resistance values have been demonstratedusing a modified version of the nail pull-through test prescribed byASTM test standard D3462, wherein the test fixture has an opening thathas been reduced from a 2.5 inch diameter to a 1.5 inch diameter. Usingthis modified test at a temperature of 72 degrees F., a shingle 74having reinforcement material 19 formed from woven polyester fabric mayhave a nail pull-through resistance value within the range of from about39 percent to about 46 percent greater than in an otherwise identicalshingle without the reinforcement material 19.

When using the modified test at a temperature of 32 degrees F., ashingle 74 having reinforcement material 19 formed from woven polyesterfabric may have a nail pull-through resistance value of at least about25 percent greater than in an otherwise identical shingle without thereinforcement material 19. Alternatively, when using the modified testat a temperature of 32 degrees F., a shingle 74 having reinforcementmaterial 19 formed from woven polyester fabric may have a nailpull-through resistance value within the range of from about 25 percentto about 37 percent greater than in an otherwise identical shinglewithout the reinforcement material 19.

Improved nail blow through values have been demonstrated in shingles 74relative to otherwise identical shingles without the reinforcementmaterial 19. To test nail blow through, a shingle 74 was placed onoriented strand board and a nail was driven into the shingle 74 using anair gun at 130 psi to simulate installation on the roof, and toreplicate any nail blow through damage that may occur to the shingle 74during installation with an air gun at 130 psi. The test was conductedat room temperature or at about 72 degrees F. After the nail was driveninto the shingle 74, the shingle 74 was turned upside down, the nail wasdriven back out of the shingle 74, and any wood present was removed fromthe shingle 74 and nail hole. A second nail was inserted in the holeformed by the first nail and the shingle 74 was tested for nail pullthrough resistance using the modified test described above. Using thismethod, a shingle 74 having reinforcement material 19 formed from wovenpolyester fabric may have a nail pull-through resistance value withinthe range of from about 13 percent to about 42 percent greater than inan otherwise identical shingle without the reinforcement material 19.

Because there may be substantially no granules in the portion of theoverlay sheet 68 covered by reinforcement material 19, the weight of thelaminated shingle 74 may be reduced relative to an otherwise identicalshingle without the reinforcement material 19. For example, weight ofthe exemplary laminated shingle 74 illustrated in FIG. 2, may be reducedwithin the range of from about four percent to about six percentrelative to the weight of an otherwise identical shingle having no suchreinforcement material 19. The material and transportation costs mayalso be reduced.

As described above and shown in FIG. 1, the continuous strip ofreinforcement material 19 may be payed out from a roll 20 and adhered tothe first asphalt coated sheet 18. As described above, the embodiment ofthe woven reinforcement material 19 illustrated in FIGS. 2 and 3 mayhave a thickness of about 9.5 mils. Alternatively, the reinforcementmaterial 19 may be a woven material having a thickness within the rangeof from about 3 mils to about 20 mils, and may be too thick to bemanufactured and mounted on a roll in the manner of known PET film.

At typical roofing shingle line speeds, it is necessary for thereinforcement material to be within the range of from about 20,000 feetto about 30,000 feet long to maintain splicing intervals of within therange of from about 15 minutes to about 30 minutes. Films of about 1.5mils in thickness are typically produced on master rolls several feetwide and then slit to a desired width, such as within the range of fromabout 1.0 inch to about 1.5 inches. These slit rolls of film areconsidered dimensionally stable and easy to handle.

The embodiment of the woven reinforcement material 19 illustrated inFIGS. 2 and 3 may have a thickness of about 9.5 mils. The wovenreinforcement material 19 has compressive and tensile modulisignificantly lower than PET film. To ensure that splicing intervals ata desired level, such as within the range of from about 15 minutes toabout 30 minutes, the outside diameter (OD) of a 1.0 inch wide roll ofwoven reinforcement material 19 would be significantly larger than a 1.0inch wide roll of PET film due to the increased thickness of the wovenreinforcement material 19.

It has been shown that a length of woven reinforcement material 19 longenough to ensure that splicing intervals are within the range of fromabout 15 minutes to about 30 minutes may be provided on a spool orbobbin onto which the woven reinforcement material 19 has been appliedor wound in a waywind pattern. In a first embodiment, as shown in FIG.7, the spool 200 with the woven reinforcement material 19 installed mayhave a width W of about 10.0 inches. The woven reinforcement material 19may be wound onto the spool 200 with about 20 wraps across the 10.0 inchwidth of the spool 19, such that the wound reinforcement material 19 hasan outer diameter of about 19.0 inches. Once wound, the initial weight,i.e., the weight of the woven reinforcement material 19 before the spool200 is used in a shingle manufacturing process, is about 35 lbs. Inother embodiments, the spool 200 may hold within the range of from about30 lbs. to about 40 lbs. of the woven reinforcement material 19. Thespool may have any other desired width W, such as a width greater of atleast about 10 inches. The spool may also hold any other desired amountof the woven reinforcement material 19, such as an amount greater thanabout 30 lbs. Additionally, the reinforcement material 19 may be woundonto the spool 200 such that the wound reinforcement material 19 has anouter diameter of at least about 19.0 inches.

Alternatively, the spool 200 with the woven reinforcement material 19installed may have a width W of about 12.0 inches. The wovenreinforcement material 19 may be wound onto the spool 200 with about 24wraps across the 12.0 inch width of the spool 19, such that the woundreinforcement material 19 has an outer diameter of about 22.0 inches.The spool 200 will hold about 70 lbs of the woven reinforcement material19. In other embodiments, the spool 200 may hold within the range offrom about 65 lbs. to about 75 lbs. of the woven reinforcement material19. Advantageously, with about 70 lbs. of the woven reinforcementmaterial 19 on the spool 200, the spool 200 will run within the range offrom about 45 minutes to about 60 minutes at a speed within the range offrom about 600 ft/min to about 1000 ft/min before running out of wovenreinforcement material 19 and needing to be changed. It will beunderstood that the length of time that the spool 200 will run beforerunning out of woven reinforcement material 19 will vary with thethickness of the reinforcement material 19. It will be furtherunderstood that material, such as the woven reinforcement material 19,that has been applied to a spool in a waywind pattern may be unwoundwith little or no tangling.

It will be further understood that typical finishing operationsperformed on woven reinforcement material 19 during its manufacture addsundesirable cost to the woven reinforcement material 19. These finishingoperations may consist of scouring the fabric to remove chemicalprocessing agents. For polyester reinforcement material as describedabove, the polyester fabric may be heat-set when manufactured to reduceshrinkage when the polyester reinforcement material is applied to thehot asphalt of the first asphalt coated sheet 18. If desired, thereinforcement material 19 may be manufactured without these finishingoperations. The reinforcement material 19 that has not been scoured orheat-set may then be slit to a width wider than the width desired on thefinished laminated shingle 74 such that it shrinks to the desired widthwhen applied to the hot asphalt of the first asphalt coated sheet 18.

For example, to achieve a second or installed width of about 1.0 inch onthe finished laminated shingle 74, the reinforcement material 19 may beslit to a first or pre-installed width within the range of from about1.125 inches to about 1.25 inches. It will be understood that the amountof shrinkage of the reinforcement material during application to the hotasphalt of an asphalt coated sheet will vary with the material of thereinforcement material 19, the temperature of the asphalt, and otherfactors.

If desired, processing chemicals such as lubricants may be applied tothe reinforcement material 19 prior to its application to the hotasphalt of the first asphalt coated sheet 18. For example, a long chainsaturated hydrocarbon lubricant with surface active functionality thatis compatible with asphalt may aid in wetting out the fibers within thereinforcement material 19 by reducing the viscosity of the asphalt atthe interface of the reinforcement material 19 and the asphalt duringapplication of the reinforcement material 19. Examples of suitablelubricants include tallow amines, the reaction products of fatty acidswith an excess of polyamines, and imidazalines derived from fatty acids.

Although the embodiments above have been disclosed in the context of alaminated shingle 74, it will be understood that the reinforcementmaterial 19 may be attached to any other type of shingle, such as asingle layer shingle.

As used herein the term “asphalt” is meant to include asphalts producedfrom petroleum refining, including residua from atmosphericdistillation, from vacuum distillation, and from solvent de-asphaltingunits, recycled asphalt streams, such as re-refined motor oil bottoms.Mixtures of different asphalts can also be used. The exemplaryembodiments disclosed herein can also be used with natural bitumen, suchas the products extracted from the oil sands in Alberta or asphaltsderived from oil sands by various refinery processes.

As used herein the term “asphalt” is meant to include asphalts producedfrom petroleum refining, including residua from atmosphericdistillation, from vacuum distillation, and from solvent de-asphaltingunits, recycled asphalt streams, such as re-refined motor oil bottoms.Mixtures of different asphalts can also be used. The exemplaryembodiments disclosed herein can also be used with natural bitumen, suchas the products extracted from the oil sands in Alberta or asphaltsderived from oil sands by various refinery processes.

By “roofing shingle coating asphalt” or “coating asphalt,” as usedherein, is meant an asphalt that is suitable for use as a coatingasphalt to make asphalt roofing shingles as defined by ASTM D 3462-16: asoftening point minimum of from 190° F. (88° C.) to 320° F. (160° C.)and a penetration at 77° F. (25° C.) minimum of 15 decimillitres (dmm).This softening point is referred to herein as the “target softeningpoint”. Asphalts falling under the ASTM D 3462-16 definition of coatingasphalt are unfilled asphalts, prior to any inclusion of fillermaterials.

In other exemplary embodiments, the term “coating asphalt” meets one ormore of the tighter specifications that may be used by shinglemanufacturers. Some examples of these specifications include a softeningpoint of from 200° F. (93° C.) to 215° F. (102° C.), a penetration at77° F. (25° C.) of from 16 dmm to 22 dmm, a melt viscosity at 400° F.(204° C.) of from 150 centipoise (cps) to 450 cps, a durability ofgreater than 60 cycles in the Weatherometer, and a flashpoint of greaterthan 550° F. (288° C.). Other examples of suitable coating asphaltsinclude those with a softening point of from 212° F. (100° C.) to 220°F. (104° C.), a penetration at 77° F. (25° C.) of from 16 dmm to 20 dmm,a melt viscosity at 400° F. (204° C.) of from 275 cps to 375 cps, and aflashpoint of greater than 550° F. (288° C.). In some manufacturers'specifications, a minimum specific target penetration of 15 dmm or 17dmm is used, although there are a range of different manufacturerspecifications.

In a first aspect of the invention, a polymer-modified asphaltcomposition is provided, which comprises an asphalt material that ismodified with one or more polymers. In some exemplary embodiments, thecoating composition further comprises a secondary additive that is awax,fatty acid amide, or other viscosity reducing material. Thepolymer-modified asphalt composition has unexpectedly been found todemonstrate a unique balance between providing improved weatheringproperties, while also providing acceptable or enhanced granuleadhesion.

The asphalt material may include various types or grades of asphalt,including flux, paving grade asphalt blends, propane washed asphalt,and/or blends thereof. Effective blends of asphalt or bituminousmaterials are understood by those of ordinary skill in the art. In someexemplary embodiments, the asphalt includes one or more fillers, such asa filler of finely ground inorganic particulate matter, such as groundlimestone, dolomite or silica, talc, sand, cellulosic materials,fiberglass, calcium carbonate, or combinations thereof In some exemplaryembodiments, the one or more fillers is included in at least 10 wt. %,based on the total weight of the polymer-modified asphalt composition.In some exemplary embodiments, the one or more fillers are included inabout 20 wt. % to about 80 wt. %, including about 25 wt. % to about 75wt. %, about 30 wt. % to about 70 wt. % and about 40 to about 65 wt. %,based on the total weight of the polymer-modified asphalt composition.In some exemplary embodiments, the asphalt composition further comprisesvarious oils, fire retardant materials, and other compoundsconventionally added to asphalt compositions for roofing applications.

In some exemplary embodiments, the asphalt material has the advantage ofbeing prepared using a wide array of paving grade asphalt materials,such as different types of paving asphalts used independently or as amixture with various types of asphalt, such as, for example, solventextracted asphalt, naturally occurring asphalt, synthetic asphalt, andrecycled asphalt. Typical paving grade asphalts are straight runasphalts derived from the atmospheric and vacuum distillation of crudeoils, or are made by blending vacuum tower residua with residua fromsolvent de-asphalting units or re-refined motor oil bottoms or otherrecycled streams.

By “paving grade asphalt,” as used herein, is meant a performance gradeasphalt according to AASH2O 17320-17 that has a softening point withinthe range of about 60° F. to about 130° F. and a penetration value of atleast about 25 dmm. Paving grade asphalts are not typically used inroofing applications because such asphalts are not able to achieve theproperties required to be considered “coating grade” asphalt, as definedby ASTM D 3462-16: a softening point minimum of from 190° F. (88° C.) to235° F. (113° C.) and a penetration at 77° F. (25° C.) minimum of 15decimillimeter (dmm).

In some exemplary embodiments, the asphalt material used in the asphaltcomposition includes at least a paving-grade asphalt. Any suitablepaving-grade asphalt(s) can be used, for example paving asphalts whichmeet the PG 64-22 specifications (AASHTO M320). PG 64-22 is the mostcommon paving specification in the United States. Paving asphalts werepreviously graded by viscosity and a common asphalt that is similar tothe PG 64-22 grade asphalt and also usable in this method, is the oldAC20 grade asphalt (ASTM D 3381). Other examples of suitablepaving-grade asphalts include PG 67-22, PG 70-22, PG 58-22, PG 58-28, PG58-22, PG 70-16, PG 70-10, PG 67-10, pen grade 40/50, pen grade 60/70,pen grade 85/100, pen grade 120/150, AR4000, AR8000, and AC/30 grade.

In some exemplary embodiments, the paving grade asphalt is included inan amount from about 15 to about 80 wt. %, including about 17 wt. % toabout 50 wt. %, including about 20 wt. % to about 45 wt. %, about 22 wt.% to about 40 wt. % and about 24 to about 35 wt. %, based on the totalweight of the polymer-modified asphalt composition.

In some exemplary embodiments, one or more additives are added to thepaving-grade asphalt, including one or more polymer additive and,optionally, a secondary additive. The polymer additive(s) may includeany suitable polymer, or any suitable mixtures of different polymers. Insome exemplary embodiments, the polymer additive comprises anelastomeric radial or linear polymer. In some exemplary embodiments, thepolymer additive comprises a copolymer such as a linear or radialcopolymer. In some embodiments the polymer additive comprises one ormore of atactic polypropylene (APP), isotactic polypropylene (IPP),styrene-butadiene block copolymer (SBS), chloroprene rubber (CR),amorphous polyolefin, SBR latex, natural and reclaimed rubbers,butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), isoprenerubber (IR), styrene-polyisoprene (SI), butyl rubber, ethylene propylenerubber (EPR), ethylene propylene diene monomer rubber (EPDM),polyisobutylene (PIB), chlorinated polyethylene (CPE), styreneethylene-butylene-styrene (SEBS), hydrogenated SBS, andvinylacetate/polyethylene (EVA). In other exemplary embodiments, thepolymer additive comprises a radial polymer or a combination of linearand radial polymers. Examples of polymer modifiers are also disclosed inU.S. Pat. No. 4,738,884 to Algrim et al. and U.S. Pat. No. 3,770,559, toJackson, the contents of which are incorporated herein by reference intheir entirety. In some exemplary embodiments, the asphalt is modifiedwith styrene-butadiene block copolymer (radial SBS).

In some exemplary embodiments, the polymer additive is included in thepolymer modified coating asphalt composition in an amount from about 0.5wt. % to about 20.0 wt. %, based on the total weight of the polymermodified coating asphalt composition. In some exemplary embodiments, thepolymer additive is included in an amount from about 1.0 to about 15.0wt. %, or from about 1.5 to about 10.0 wt. %, or from about 2.0 to about7.0 wt. %, or from about 2.5 to about 6.8 wt. %, or from about or fromabout 3.0 to about 6.5 wt. %, or from about 3.5 to about 6.2 wt. %, orfrom about 5.5 to about 6.15 wt. %, based on the total weight of thepolymer modified coating asphalt composition. In some exemplaryembodiments, the polymer additive is included in the polymer modifiedcoating composition in an amount of about 6.0 wt. %, based on the totalweight of the polymer modified coating asphalt composition.

Non-coating grade asphalts, such as paving-grade asphalt, have softeningpoints, penetration values, and melt-viscosities that are not optimalfor coating compositions. As such, non-coating grade asphalt will oftenbe air-blown to raise the softening point, lower the penetration value,and raise the melt viscosity, so that the asphalt can be used forcoating roofing products. This air-blowing process increases thesoftening point of the asphalt. Other times the paving grade asphaltwill be partially-blown or “under-blown” to help reduce loss ofmaterial, known as “blow loss” associated with the oxidation process.Such “under-blown” asphalt materials then require the addition of ablowing catalyst, such as phosphoric acid, ferric chloride, phosphoruspentoxide, aluminum chloride, hydrohalic acid, and boric acid and a waxto obtain the desired coating grade asphalt properties, such as thatdescribed in U.S. Pat. No. 7,951,239, the disclosure of which isincorporated by reference herein in its entirety.

The use of oxidized asphalt with polymer additives, however, has anumber of drawbacks. First, oxidized asphalt does not react well withsome polymers, such as SBS, and is thus often not suitable inpolymer-modified asphalt compositions. Thus, in some exemplaryembodiments, the asphalt in the present invention is not oxidized orblown. In other exemplary embodiments, the asphalt is no greater than50% oxidized, such as no greater than 30% oxidized, no greater than 20%oxidized, no greater than 10% oxidized, no greater than 5% oxidized, andno greater than 1% oxidized.

In some exemplary embodiments, the secondary additive is a viscosityreducing agent, such as one or more of a wax, a fatty acid ester, afatty acid ester salt, and/or a fatty acid amide. In some exemplaryembodiments, the paving-grade asphalt material is heated and mixed sothat the polymer and homogenously blend together. The polymer and thesecondary additive do not react or crosslink, and simply form apolymer/secondary additive blend. In some exemplary embodiments, afterblending the polymer modifier and secondary additive into the asphalt,the asphalt composition achieves penetration and softening point valuesthat meet the target ranges for these values in a coating-grade asphalt.

Any type of wax, or a mixture of different waxes, capable of functioningas described herein can be used in the method. In one exemplaryembodiment, the wax has a high congealing point or a high drop meltpoint of at least about 75° C., specifically at least about 90° C., andmore specifically at least about 100° C. When referring to wax testing,the term “melt point” refers broadly to either congealing point or dropmelt point, which are defined by ASTM D 938 in the case of congealingpoint and ASTM D 3954 in the case of drop melt point. Also, wax can becharacterized by penetration or hardness (ASTM D5 or ASTM D 1321),density (ASTM D1505), viscosity (ASTM D 4402 or ASTM D88), or acid value(ASTM D 1386).

In some exemplary embodiments, the wax is one or more of a paraffin waxand a non-paraffin wax. Paraffin waxes typically have melting pointsbelow 70° C. and have less than 45 carbon atoms. Non-paraffin waxestypically have melting points above 70° C. and have more than 45 carbonatoms. The non-paraffin wax can be one or more of a natural wax, amodified natural wax, a partial synthetic wax, and a full synthetic wax.Non-limiting examples of suitable partial and fully synthetic waxesinclude ethylene bis-stearamide wax (EBS), Fischer-Tropsch wax (ET),oxidized Fischer-Tropsch wax (FTO), stearic acid pitch, polyolefin waxessuch as polyethylene wax (PE), oxidized polyethylene wax (PEO),polypropylene wax, polypropylene/polyethylene wax, alcohol wax, siliconewax, petroleum waxes such as microcyrsatlline wax, and chlorinated wax.Any suitable mixtures of different waxes can also be used. For example,the wax can include a blend of a Fischer-Tropsch wax and a polyethylenewax. In some exemplary embodiments, the wax is a non-paraffinic wax witha high melting point (greater than 70° C.). In various exemplaryembodiments, the wax has a melting point of at least 100° C., such as atleast 120° C., or at least 130° C., or at least 140° C.

In some exemplary embodiments, the wax is a naturally occurring wax canbe derived from a plant, animal or mineral. Some examples of naturalwaxes that may be suitable include plant waxes such as candelilla wax,carnauba wax, rice wax, Japan wax and jojoba oil; animal waxes such asbeeswax, lanolin and whale wax; and mineral waxes such as montan wax,ozokerite and ceresin.

In some exemplary embodiments, the secondary additive comprises at leastethylene bistearamide (EBS), which has a melt point of 140 to 146° C., apenetration hardness at 25° C. of about 1 dmm, a density of from about(8.49 lbs/gal), and an acid number of 4. EBS is a brittle wax-like solidformed from the reaction of an amine with hydroxystearic acid. Theformed hydroxystearamide is a high melting point wax-like material thatis extremely resistant to acids and alkalis in contrast to natural andsynthetic ester waxes.

In some exemplary embodiments, the secondary additive comprises a saltof a fatty acid ester, such as a fatty acid ester derived from a plantor animal.

Alternatively, or in addition, the secondary additive is aFischer-Tropsch wax with a melt point of greater than 100° C. and ahardness at 25° C. from 1 dmm to a value so soft that it could not bemeasured by the techniques in ASTM D5. In another exemplary embodiment,the secondary additive is a polyethylene wax with a melt point of from100 to 125° C., a hardness at 25° C. of from 1 to 7 dmm, a density offrom 0.91 to 0.95 gm/cc, a viscosity of from 20 to 450 cps at 140° C.,and a nil acid number. In another exemplary embodiment, the wax is anoxidized polyethylene wax with melt point of from 135 to 140° C., ahardness at 25 C of <0.5 dmm, a viscosity of from 3600 to 4500 cps at150° C., and acid number of 30.

In some exemplary embodiments, the secondary additive is one or morefatty acid amides. Fatty acid amides are amides produced from thereaction of a fatty acid and an amine. The fatty acid amide can be amonoamide, a substituted amide, a bisamide, a methylol amide, an esteramide, an alkyl urea, and the like. Non-limiting examples of suitablefatty acid amides include oleamide, stearamide, erucamide, behenamide,N-oleylpalmitamide, N-stearylerucamide, ethylene bis-stearamide (EBS),and ethylene bis-oleamide.

In some exemplary embodiments, the secondary additive is included in thepolymer modified coating asphalt composition in an amount from about0.01 wt. % to about 20.0 wt. %, based on the total weight of the polymermodified coating asphalt composition. In some exemplary embodiments, thesecondary additive is included in an amount from about 0.5 to about 15.0wt. %, or from about 1.0 to about 10.0 wt. %, or from about 1.2 to about7.0 wt. %, or from about 1.5 to about 5.0 wt. %, or from about 1.6 toabout 3.0 wt. %, or from about 1.7 to about 2.5 wt. %, or from about1.75 to about 2.4 wt. %, or from about 1.8 to about 2.3 wt. %, or fromabout 1.85 to about 2.2 wt. %, or from about 1.90 to about 2.15 wt. %,or from about 1.95 to about 2.10 wt. %, or from about 1.98 to about 2.05wt. %, based on the total weight of the polymer modified coating asphaltcomposition. In some exemplary embodiments, the secondary additive isincluded in the polymer modified coating asphalt composition in anamount of about 2.0, based on the total weight of the polymer modifiedcoating asphalt composition.

In some exemplary embodiments, the resulting polymer modified coatingasphalt may comprise about 60 to about 99 wt. % of a paving gradeasphalt, about 1 to about 10 weight percent of a polymer additive, and0.5 to about 8.0 weight percent of the secondary additive, based on thetotal weight of the polymer modified coating asphalt. In some exemplaryembodiments, the polymer modified coating asphalt comprises about 80 toabout 95 wt. % of a paving grade asphalt, about 2 to about 7 weightpercent polymer additive, and about 2.0 to about 5.0 weight percentsecondary additive, based on the total weight of the polymer modifiedcoating asphalt. In some exemplary embodiments, the polymer modifiedcoating asphalt comprises about 80 to about 95 wt. % of a paving gradeasphalt, about 1 to about 8 weight percent polymer additive, and about1.85 to about 2.4 weight percent secondary additive, based on the totalweight of the polymer modified coating asphalt. In some exemplaryembodiments, the polymer modified coating asphalt comprises about 80 toabout 95 wt. % of a paving grade asphalt, about 1 to about 8 weightpercent polymer additive, and about 1.9 to about 2.4 weight percentsecondary additive, based on the total weight of the polymer modifiedcoating asphalt. A filler may then be added to the polymer modifiedasphalt composition, such that the filled asphalt composition comprisesabout 30 to 80 wt. % of filler material and about 20 to 70 wt. % of thepolymer modified asphalt composition. In some exemplary embodiments, thefilled asphalt composition comprises about 45 to 70 wt. % of fillermaterial and about 30 to 55 wt. % of the polymer modified asphaltcomposition.

Table 1, below, outlines exemplary polymer modified asphaltcompositions, in accordance with the present inventive concepts.

TABLE 1 Exemplary Exemplary Exemplary Ingredient Comp. 1 Comp. 2 Comp. 3Paving Grade Asphalt 15 to 80 wt. % 20-40 wt. % 24-30 wt. % Filler 20-80wt. % 45-70 wt. % 62-68 wt. % Polymer additive 2.0-7.0 wt. % 3.5-6.5 wt.% 6.0 wt. % Secondary additive 1.8-2.5 wt. % 1.85-2.45 wt. % 2.0 wt. %

Although SBS-type polymers are often used to modify asphalt to makecoatings for various roofing products, the butadiene portion of thepolymer is susceptible to chain-scission when exposed to UV-light fromthe sun. Accordingly, in such instances, the coating must be protectedwith an opaque mineral surfacing or some other form of additionalcoating layer to protect the polymer modified asphalt. However, it hasbeen discovered that the secondary additive creates a protective layerover a shingle when included in an asphalt-based coating composition.This protective layer is created by the secondary additive “blooming” tothe surface of the coating, preserving the asphalt coating below. Thisprotective coating protects the butadiene portion of the polymer fromUV-light, which reduces or eliminates the need protect the asphaltcoating with any additional surfacing layers.

Other materials suitable for use in the asphalt composition includetackifying resins and other types of natural and synthetic rubbermaterials and thermoplastic polymers. Additionally, recycled rooftear-off materials, such as shingles, may be included in the asphaltcomposition. Recycled shingles may be processed in a wide variety ofdifferent ways to allow the material to be used in the composition.

In some exemplary embodiments, addition of the polymer additive andsecondary additive alters the physical properties the paving gradeasphalt to transform it into a suitable coating grade asphalt that canbe using in roofing applications. In some exemplary embodiments,addition of the polymer additive and secondary additive results in anasphalt composition that has a final softening point of about 185° F. toabout 250° F. This range is referred to herein as the “target softeningpoint range.” In some exemplary embodiments, addition of the polymer andadditive results in an asphalt composition that has a softening point offrom 190° F. to about 240° F., or from 200° F. to about 230° F.

In some exemplary embodiments, the secondary additive helps thenon-coating grade asphalt to reach the target pen range, which isbetween about 15 to 50 dmm, including about 17 to 40 dmm, and about 20to 35 dmm.

In some exemplary aspects of the subject invention, the polymer modifiedasphalt composition is used to manufacture an impact resistant shingle.The impact resistant shingle comprises one or more substrates and anasphalt coating composition that is applied to one or both sides of theone or more substrates. In some exemplary embodiments, the coatingcomposition contains asphalt that is modified with one or more polymeradditives. In some exemplary embodiments, the asphalt compositionfurther comprises a secondary additive that may be a wax, fatty acidamide, or other viscosity reducing agent. In some exemplary embodiments,the coating composition provides impact resistance to the shingle.

The substrate used in the impact resistant shingle is not particularlylimited and can be any material typically used in the roofing industry.In some exemplary embodiments, the substrate may be a fibrousreinforcement layer, such as chopped strand mats, continuous strandmats, swirl mats, woven and non-woven fabrics, e.g., woven rovings,insect screening, scrim and the like. In some exemplary embodiments, thefibrous materials are glass but they may also be organic polymericmaterials or combinations of glass and organic polymers.

In some exemplary embodiments, this reinforcing base material serves asa matrix to support an asphalt coating and gives the shingle strength.

The secondary additives described in the exemplary embodiments hereinhave a number of important functions. In some exemplary embodiments, thesecondary additive imparts increased impact resistance to the shingle,without the addition of separate or additional substrate layers. In someexemplary embodiments, the secondary additive increases the adhesion ofgranules on top of the shingle. In other exemplary embodiments, thesecondary additive increases the tensile and tear strengths of theshingle itself. For instance, shingles coated with the polymer modifiedasphalt coating composition disclosed herein demonstrated an increase ofat least 5%, or at least 8%, or at least 10%, compared to a shinglecoated with an otherwise identical polymer modified asphalt compositionexcluding the secondary additive. In some exemplary embodiments, theadditive also helps to increase the creep value of the asphalt coating.

Additionally, the polymer modified asphalt composition according to thepresent inventive concepts demonstrates improved stability, as shown byASTM D7173-11 “Standard Practice for Determining the Separation Tendencyof Polymer from Polymer Modified Asphalt”. Coatings using a polymermodifier separate to a greater or lesser extent depending on thecompatibility of a given polymer with the a given asphalt. The presenceof the secondary additive has been found to stabilize the asphalt blend.

Additionally, the coatings with wax/polymer presented no stain whentested by ASTM D2746-07(2013) “Standard Test Method for StainingTendency of Asphalt (Stain Index)”. Per the standard, “this test methodmeasures the tendency for oil components to separate spontaneously fromasphalt. The separation of oil components can cause staining in asphaltroofing products and adjacent materials in storage and use. The stainindex is related to the thermal stability of the asphalt. Higher stainindex values indicate lower stability and greater tendency forstaining.” The polymer modified asphalt coating composition has zerostain due to the fact that the secondary additive makes the polymer andasphalt compatible.

Conventional products that are designed to provide impact resistance usean integrated polymeric backing, typically on the underside of theshingle. Such a product is illustrated in U.S. Patent Application No.09/223,578, which is incorporated herein by reference. While thispolymeric backing imparts the necessary impact resistance, such abacking is expensive, adds complexity to the manufacturing process, andresults in various process limitations. Additionally, a significantamount of waste and side-products are produced during application andmanufacture of the polymeric backing and the roofing material made withthe polymeric backing. The products according to the exemplaryembodiments disclosed herein, however, do not require this polymericbacking, thereby reducing overall cost and simplifying the manufacturingprocess. Accordingly, in some exemplary embodiments, roofing materialsmanufactured in accordance with the subject invention are free of anypolymeric backing material.

The improved impact resistance of the roofing materials of the presentinvention is demonstrated by a standard method, UL 2218, “Standard forImpact Resistance of Prepared Roof Covering Materials”, UnderwritersLaboratories, May 31, 1996. In this method, the roofing material issecured to a test deck and a steel ball is dropped vertically through atube onto the upper surface of the roofing material. The roofingmaterial can be tested at four different impact force levels: Class 1(the lowest impact force) through Class 4 (the highest impact force).The force of impact in the different classes is varied by changing thediameter and weight of the steel ball, and the distance the ball isdropped. For example, the Class 1 test uses a steel ball having adiameter of 1.25 inches (32 mm) weighing 0.28 pounds (127 g) that isdropped a distance of 12 feet (3.7 m), while the Class 4 test uses asteel ball having a diameter of 2 inches (51 mm) weighing 1.15 pounds(521 g) that is dropped a distance of 20 feet (6.1 meters). After theimpact, the roofing material is inverted and bent over a mandrel in boththe machine and cross directions, and the lower surface of the roofingmaterial is examined visually for any evidence of an opening or tear. A5× magnification device may be used to facilitate the examination of theroofing material. If no evidence of an opening is found, the roofingmaterial passes the impact resistance test at the UL 2218 class tested.A roofing material having a secondary additive according to the presentinventive concepts demonstrated an increased impact resistance of atleast two UL 2218 classes compared with the same roofing materialwithout the secondary additive. In some exemplary embodiments, theroofing material made in accordance with the present exemplaryembodiments meets at least the UL2218 Class 3 impact resistancestandard, and in some exemplary embodiments, meets the UL 2218 Class 4impact resistance standard.

It has been discovered that the inclusion of the secondary additiveprovides the additional benefit of significantly improved weatheringproperties, compared to otherwise identical asphalt compositionsexcluding the secondary additive, or including an additive in an amountless than 1.8 wt. %.

The inventors have further discovered a particular concentration ofsecondary additive that provides the above-described improved weatheringproperties, while maintaining, or improving granule adhesion.Particularly, the addition of the secondary additive in an amount fromabout 1.85 wt. % to less than about 2.5 wt. % provides improvedweatherability, with no negative impact on granule adhesion as comparedto an otherwise identical shingle made with a conventional oxidizedasphalt coating. In contrast, secondary additive amounts over about 3.0wt. % can cause the granule adhesion to drop.

Furthermore, the secondary additive has been unexpectedly found tosubstantially lower the viscosity of the asphalt composition, comparedto a conventional oxidized asphalt coating composition.

As illustrated below in Table 2, a conventional oxidized asphalt coatingcomposition has a rotational viscosity at 325 F of 31,883 cP and anSBS-modified paving-grade asphalt has a rotational viscosity at 325 F of19,143 cP. In contrast, the addition of a wax, such as vistowax or lonzawax, demonstrated a reduction in viscosity by over three times that ofan otherwise similar asphalt composition without the wax additive. Eachof the asphalt compositions below in Table 2 include 62% limestonefiller. This reduction in viscosity is further illustrated in FIG. 8.

TABLE 2 SBS/2.0 wt. % Polyethylene wax SBS/2.0 wt. % EBS all SBS Batchw/ w/ PG 64-22 wax w/PG 64-22 Control-oxidized PG 64-22 (paving (pavinggrade (paving grade Type Asphalt Coating. grade) asphalt) asphalt)Rotational Viscosity 31883 19143 4958 3525 325° F. (cP): RotationalViscosity 12350 7200 2475 1900 350° F. (cP): Rotational Viscosity 51333983 1183 750 375° F. (cP): Rotational Viscosity 2550 2458 725 625 400°F. (cP):

In some exemplary embodiments, the polymer modified coating asphalt isprepared by the following method. The necessary amount of asphalt andpolymer additive are mixed together under a high shear mixer (an exampleof which includes a Silverson Lab mixer) over heat (about 380° F.). Oncethe polymer added has fully mixed with the asphalt, the secondaryadditive is slowly added under a low shear mixer (less than 600 rpm) andthe mixture is mixed under the low shear for about 2-4 hours at 380° F.The filler is then added and mixed for an additional 10-30 minutes underthe low shear. The mixture is then allowed to cool to 310° F. or less.

All combinations of method or process steps as used herein can beperformed in any order, unless otherwise specified or clearly implied tothe contrary by the context in which the referenced combination is made.

While various inventive aspects, concepts and features of the inventionsmay be described and illustrated herein as embodied in combination inthe exemplary embodiments, these various aspects, concepts and featuresmay be used in many alternative embodiments, either individually or invarious combinations and sub-combinations thereof. Unless expresslyexcluded herein all such combinations and sub-combinations are intendedto be within the scope of the present inventions.

EXAMPLES

The following examples are included for purposes of illustration and arenot intended to limit the scope of the methods described herein.

Example 1

Physical testing was conducted on the inventive polymer-modified asphaltcompositions to measure physical properties of the asphalt. An asphaltcomposition according to Tables 3 and 4 was prepared and physicalproperties were measured before addition of the secondary additive,while the asphalt composition was blended with the secondary additive,and after addition of a limestone filler. The results are listed in thetables that follow. PG 64-22 Whiting is a paving grade asphalt bindercommercially available from BP. Calprene 411 is a 70/30butadiene/styrene thermoplastic copolymer (radial polymer) that has beenpolymerized in solution and is commercially available from Dynasol.Lonza EBS wax is a low-density polyethylene wax (N,N′ EthyleneBisstearamide) commercially available from Lonza.

TABLE 3 Concentration (based on total weight Ingredient of the polymermodified asphalt) PG 64-22 Whiting Asphalt Binder  92 wt. % Calprene 4115.0 wt. % Lonza wax 3.0 wt. %

TABLE 4 Concentration (based on total weight Ingredient of the asphaltcomposition) Polymer modified asphalt 38 wt. % Limestone filler 62 wt. %

Table 5 illustrates the results for physical tests run on paving gradeasphalt composition with no wax additive or radial polymer.

TABLE 5 Softening Point 119° F. Pen at 77° F. 62.0 dmm

Table 6 shows the results for physical tests run on the asphaltcomposition while it was blended with the wax additive and radialpolymer. The asphalt composition was blended together for five hours at380° F.

TABLE 6 Softening Point 214° F. Pen at 77° F. 46.0 dmm

The results in Table 6 show that as the radial polymer and wax additiveare being added to the asphalt composition that the physical propertiesare beginning to improve. Particularly, the softening point increasedand the pen dropped significantly.

Table 7 illustrates the results for the physical tests run on theasphalt composition after five hours when the composition had been fullyblended and heated. Additionally, the limestone filler was added andfully integrated into the composition.

TABLE 7 Softening Point 241° F. Pen at 77° F. 16.0 dmm

The results in Table 7 show that after the wax additive and radialpolymer have had sufficient time to blend with the asphalt and fillermaterial, the softening point significantly increased and the pensignificantly decreased, as compared to both the base asphalt physicalproperties and the physical properties of the asphalt composition beforethe addition of the filler material. The softening point of 241° F. andpen of 16.0 dmm are both within the target ranges for a suitable coatinggrade asphalt.

Example 2

An asphalt composition according to Tables 8 and 9 was prepared andphysical properties were measured before addition of a wax additive,while the asphalt composition was blended with the additive, and afterthe addition of a limestone filler. The results are listed in the tablesthat follow. Sasobit wax is a synthetically produced Fischer-Tropsch(FT) wax commercially available from Sasol.

TABLE 8 Concentration (based on total weight of the polymer modifiedasphalt Ingredient composition) PG 64-22 Whiting Asphalt Binder 92 wt. %Calprene 411 5.0 w. % Sasobit wax 3.0 wt. %

TABLE 9 Concentration (based on total weight Ingredient of the asphaltcomposition) Polymer modified asphalt 38 wt. % Limestone filler 62 wt. %

Table 10 shows the results for physical tests run on the base pavinggrade asphalt composition with no wax additive or radial polymer.

TABLE 10 Softening Point 119° F. Pen at 77° F. 62.0 dmm

Table 11 shows the results for physical tests run on the asphaltcomposition while it was blended with the wax additive and radialpolymer. The asphalt composition was blended together for five hours at380° F.

TABLE 11 Softening Point 208° F. Pen at 77° F. 18.0 dmm

Table 12 shows the results for the physical tests run on the asphaltcomposition after five hours when the composition had been fully blendedwith the limestone filler.

TABLE 12 Softening Point 216° F. Pen at 77° F. 14.0 dmm

The results in Table 12 show that after the wax additive and radialpolymer have had sufficient time to blend with the asphalt and fillermaterial, the softening point is significantly increased and the pen issignificantly decreased as compared to both the base asphalt physicalproperties and the physical properties of the asphalt composition beforethe addition of the filler material. The softening point of 216° F. andpen of 14.0 dmm are both within the target ranges for a suitable coatinggrade asphalt.

Example 3

Additional physical testing was conducted on the inventivepolymer-modified asphalt compositions to measure the durability andweatherability of the asphalt. One method of testing the durability ofan asphalt composition is known as a “spark test,” outlined in ASTMD1670. The spark test measures the extent of cracking and/or pitting ofasphalt films to determine the extent of deterioration that occurs dueto weathering. Various asphalt compositions were applied to anelectrically conductive backing, such as an aluminum panel, and exposedto accelerated weathering caused by UV lighting and controlledconditions of humidity, moisture, and temperature. Throughout theweathering, the asphalt film may crack, which will expose the aluminumbacking. A spark probe is then used to conduct a current in variouslocations of the panel. The probe will be able to conduct a current atany point in the asphalt film that has cracked in response to theweathering. Conventional coating asphalts are desired to pass 60 days orcycles of accelerated weathering prior to showing signs of degradation.

The results of the spark test indicated that the addition of ethylenebistearamide (EBS) as the secondary additive greatly improved the SBSpolymer modified coating's resistance to the effects of UV light andheat, yielding a coating that performed essentially as well asconventional oxidized asphalt coating at the same application levelsunder the same test conditions.

FIG. 9 illustrates an aluminum panel substrate coated with aconventional oxidized asphalt coating composition. The coatingcomposition lasted 108.5 days in the weatherometer, before failure(defined as the appearance of cracks over at least 10% of the panel).Similarly FIG. 10 illustrates an aluminum panel coated with a polymermodified coating asphalt composition in accordance with the presentinventive concepts that includes 5 weight percent of Calprene 411polymer (70/30 butadiene/styrene thermoplastic copolymer) and 3.0 weightpercent of Lonza EBS wax. The coating composition in FIG. 10 lasted 94.4days prior to failure, which passes the desired weathering parameters inthe industry.

FIGS. 11 and 12 illustrate the weatherometer results based on an asphaltcoating composition comprising non-oxidized asphalt. FIG. 11 illustratesan aluminum panel substrate coated with a non-oxidized asphalt modifiedwith 6.6 weight percent Calprene 411 only, after 14 days of weathering.The samples in FIG. 11 failed after 14 days in the weatherometer.Similarly, FIG. 12 illustrates aluminum panel substrates coated with anon-oxidized asphalt modified with 5% Calprene 411 and 3.0 wt. % ofVestoWax, which is a polyethylene wax. The samples in FIG. 12 failedafter 14 days in the weatherometer. Accordingly, it can be seen that notevery secondary additive will provide improved weathering properties. Ithas been discovered that the use of EBS and/or salts of animal orvegetable fatty acid esters as secondary additives surprisingly providethis added improvement.

Table 13, below, provides weatherometer results comparing theweatherability of a 100% oxidized coating asphalt composition (SampleA), with compositions that comprise non-oxidized paving grade asphalt(PG 64-22), along with a radial SBS additive and 2 or 3 wt. % of a waxadditive. The results provide the days to failure, which is defined asthe number of days that the sample was in the weatherometer before atleast 10% of the sample cracked. As illustrated below, Sample A (100%oxidized coating asphalt), was in the weatherometer for 108.5 days,prior to failure. In contrast, Samples B, C, E, and F, includingnon-oxidized paving grade asphalt and 5 or 6 wt. % radial SBS polymeradditive, showed very low weatherability, with days to failure less than23. When a secondary additive is included in an amount of 2.0 or 3.0 wt.%, the weatherability increased to at least 50 days, in some instancesat least 78 days, and in some instances at least 110 days. In Examples Jand M, the samples including non-oxidized paving grade asphalt, 6.0 wt.% radial SBS polymer, and 2.0 wt. % wax demonstrated a weatherabilitygreater than 130 days until failure, which is significantly improvedover both oxidized coating asphalt compositions and non-oxidized pavinggrade asphalt with only radial SBS additive compositions.

TABLE 13 A B C D E F G H I J K L M Oxidized 100% asphalt PG 64- 93.4%92%  92%  92%  92%  92%  92%  92%  92%  92%  92%  22 PG 67- 94%  22Radial 6.6 5% 5% 6% 5% 5% 6% 6% 6% 6% 6% 6% SBS EBS wax 3% 3% 2% 2% 2%Vistowax Sasobit 2% 2% 2% wax Days to 108.5 14 14 94.4 22.8 22.8 78 86.479.8 130+ 53.82 112.8 130+ Failure

Further physical testing was conducted on the inventive polymer-modifiedasphalt compositions to measure the compositions' ability to adhere andmaintain granules on a shingle. Granule adhesion is tested according toASTM D4977 (the “scrub test”). The various asphalt composition accordingto Tables 14 and 15 were prepared and applied to a reinforcementmaterial. Granules were then applied to each sample and the samples werescrubbed using a steel bristled brush at various press pressures. Thesurfaces of each sample were then scrubbed using a steel bristled brush.The shingle samples were weighed before and after the scrub test andTables 14 and 15 report the average weight loss for each sample. PG64-22 Whiting is a paving grade asphalt binder commercially availablefrom BP. EBS wax is a low-density polyethylene wax (N,N′ EthyleneBisstearamide) commercially available from Lonza.

TABLE 14 Coating Description Sample 4: Sample 2: Sample 3: PG PG 64-22 +Sample 1: PG 64-22 + 64-22 + 5 wt. % 5 wt. % Oxidized 6.6 wt. % SBS +SBS + 3 wt. % Asphalt Coating SBS 3 wt. % EBS Vistawax Press 20 50 80 2050 80 50 20 50 80 (lb) Average 1.50 0.70 0.53 1.05 0.54 0.42 0.75 1.280.87 0.68 (g) Stdev 0.35 0.13 0.14 0.35 0.15 0.09 0.15 0.41 0.22 0.19

Table—illustrates that at scrub press pressures of 20 lbs, Sample 4resulted in only 1.28 g weight loss, while the oxidized asphalt coatingdemonstrated a weight loss of 1.50 g.

However, as shown below in Table 3, a secondary additive concentrationat 2.0 wt. % appears to provide an unexpected improvement in granuleadhesion, compared to an oxidized asphalt coating composition, at thesame scrub test pressure.

TABLE 15 PG 64-22 with 6.0 wt. % SBS and 2.0 wt. % Fisher Tropsch waxOxidized Asphalt Coating (Sasobit wax) Average mass loss 0.768 g 0.15 gStd. Deviation 0.2289 0.0365

Enhanced Performance of Polymer and Secondary Additive Modified AsphaltShingle having a Reinforcement Material

In one exemplary embodiment, a reinforcement material 19, such as any ofthe reinforcements materials described above, and a polymer modifiedasphalt, such as any of the polymer modified asphalts described above,are selected and combined in a shingle to enhance the mechanicalproperties of the shingle. For example, the shingle with reinforcementmaterial 19 and polymer modified asphalt can have enhanced propertiescompared to shingles having the same reinforcement, but the shingle ismade with an oxidized asphalt (i.e. not a polymer modified asphalt). Theshingle can comprise one or more of any of the reinforcement materialsdescribed herein and one or more of any of the polymer modified asphaltcompositions disclosed herein.

In one exemplary embodiment, the reinforcement material 19 of theimproved polymer modified asphalt/reinforcement material shingle can beformed from woven polyester fabric. In one exemplary embodiment, theshingles having the reinforcement material 19 and a polymer modifiedasphalt and a compared otherwise identical shingle having the samereinforcement material and a conventional oxidized asphalt have a weightof 190-230, such as 200-220, such as 210-215, such as an approximateweight of 213 lbs per square. In one exemplary embodiment, the polymermodified asphalt comprises (prior to addition of any filler):

-   -   85-99%, such as 87-97%, such as 89-95%, such as 91-93%, such as        about 92% Asphalt;    -   0-13%, such as 1-11%, such as 3-9%, such as 5-7%, such as about        6% styrene-butadiene rubber (SBS); and    -   0-6%, such as 0.5-5%, such as 1-3%, such as 1.9-2.4%, such as        about 2% wax, such as any of the waxes disclosed herein. In one        exemplary embodiment, the wax is a polyethylene wax.

Optionally, a filler can be included in the polymer modified asphalt(and the same amount in the compared oxidized asphalt shingle) of theshingle with improved nail pull-through resistance. The filler can takea wide variety of different forms. For example, the filler can be any ofthe fillers disclosed in the present patent application. A widedifferent amounts of filler can be included in the polymer modifiedasphalt. For example, the filler to polymer modified asphalt blend canbe (based on the total weight of the polymer modified asphalt and fillerblend):

-   -   0-100%, such as 20-50%, such as 25-45%, such as 30-40%, such as        about 34% polymer modified asphalt; and    -   0-100%, such as 50-80%, such as 55-70%, such as about 66%        filler. In one exemplary embodiment, the filler is a limestone        filler.

Enhanced Nail Pull for Polymer and Secondary Additive Modified AsphaltShingle having a Reinforcement Material

In one exemplary embodiment, the nail pull-through resistance of ashingle having a reinforcement material 19, such as any of thereinforcement materials described above, and a polymer modified asphalt,such as any of the polymer modified asphalts described above is greaterthan the nail pull-through resistance of an otherwise identical shinglemade with a conventional oxidized asphalt (i.e. not a polymer modifiedasphalt).

Improved nail pull-through resistance values of a shingle having areinforcement material 19, such as any of the reinforcement materialsdescribed above, and a polymer modified asphalt, such as any of thepolymer modified asphalts described above v. a shingle having the samereinforcement material and a conventional oxidized asphalt have beendemonstrated using a modified version of the nail pull-through testprescribed by ASTM test standard D3462, wherein the test fixture has anopening that has been reduced from a 2.5 inch diameter to a 2.0 inchdiameter. For example, nail pull-through resistance values of a shinglehaving a reinforcement material 19 and a polymer modified asphalt v. anotherwise identical shingle having the same reinforcement material and aconventional oxidized asphalt can be a greater than 5% nail pull throughforce increase, a greater than 10% nail pull through force increase, agreater than 12% nail pull through force increase, at least a 14% nailpull through force increase, or an at least about 15% nail pull throughforce increase. In one exemplary embodiment, the nail pull resistance ofthe improved polymer modified asphalt/reinforcement material shingle isbetween 63-74, such as 65-71 lbf, such as 67-69 lbf, such as about 68lbf. In one exemplary embodiment, the enhanced nail pull resistancedescribed above is at room temperature (for both the PMA +Reinforcementshingle and the compared conventional asphalt plus reinforcementshingle), such as 73 degrees F. or about 73 degrees F.

Enhanced Longitudinal Adhesion for Polymer and Secondary AdditiveModified Asphalt Shingle having a Reinforcement Material

In one exemplary embodiment, the longitudinal adhesion of a shinglehaving a reinforcement material 19, such as any of the reinforcementmaterials described above, and a polymer modified asphalt, such as anyof the polymer modified asphalts described above is greater than thelongitudinal adhesion of an otherwise identical shingle made with aconventional oxidized asphalt (i.e. not a polymer modified asphalt). Asused herein, the term “longitudinal adhesion” refers to the forceapplied in the machine direction (i.e. in the direction of the length ofthe reinforcement material) required to peel the reinforcement materialoff of the shingle.

Improved longitudinal adhesion values of a shingle having areinforcement material 19, such as any of the reinforcement materialsdescribed above, and a polymer modified asphalt, such as any of thepolymer modified asphalts described above v. a shingle having the samereinforcement material and a conventional oxidized asphalt have beendemonstrated using a modified version of the peel test prescribed byASTM test standard D1876. For example, referring to FIGS. 13 and 14, asample 1200 is cut from a shingle. The sample 1200 can be cut along thecommon bond area 1202 of the shingle, with the reinforcement 19 runningthrough the center of the sample 1200. Approximately 1″ of thereinforcement material 19 is pulled up as indicated by arrow 1204. Thereinforcement material 19 can be creased to form a T-shaped sample (SeeFIG. 14). The upward extending reinforcement material 19 and the shinglematerial 1206 are pulled relatively apart in the machine directionindicated by arrows 1208, 1210 to peel the reinforcement material 19 offthe shingle material 1206. For example, the reinforcement material 19and the shingle material 1206 can be pulled relatively apart in themachine direction at a rate of 12″/min. The reinforcement material 19and the shingle material 1206 can be pulled apart for a total pulllength of 3.5″. In one exemplary embodiment, the average pull force iscomputed using the pull force data from a 1″ pull length mark to a 2″pull length mark. This area (between 1″ and 2″ of pull) is relativelysteady and not influenced by contact with the clamps that hold thereinforcement material 19 and the shingle material 1206. For example, anincrease in longitudinal adhesion values of a shingle having areinforcement material 19 and a polymer modified asphalt v. an otherwiseidentical shingle having the same reinforcement material and aconventional oxidized asphalt can be a greater than 10% increase in pullforce, a greater than 20% increase in pull force, a greater than 30%increase in pull force, a greater than 40% increase in pull force, or anat least about 45% increase in pull force. In one exemplary embodiment,the longitudinal adhesion of the improved polymer modifiedasphalt/reinforcement material shingle is greater than 1.25 lbf, such asbetween 1.25 and 2.75 lbf, such as 1.5-2.5 lbf, such as 1.75-2.25 lbf,such as about 2 lbf. In one exemplary embodiment, the enhancedlongitudinal adhesion described above is at room temperature (for boththe PMA +Reinforcement shingle and the compared conventional asphaltplus reinforcement shingle), such as 73 degrees F. or about 73 degreesF.

Enhanced Transverse Adhesion for Polymer and Secondary Additive ModifiedAsphalt Shingle having a Reinforcement Material

In one exemplary embodiment, the transverse adhesion of a shingle havinga reinforcement material 19, such as any of the reinforcement materialsdescribed above, and a polymer modified asphalt, such as any of thepolymer modified asphalts described above is greater than the transverseadhesion of an otherwise identical shingle made with a conventionaloxidized asphalt (i.e. not a polymer modified asphalt). As used herein,the term “transverse adhesion” refers to the force applied in thecross-machine direction (i.e. in the direction perpendicular to thelength of the reinforcement material) required to peel the reinforcementmaterial off of the shingle.

Improved transverse adhesion values of a shingle having a reinforcementmaterial 19, such as any of the reinforcement materials described above,and a polymer modified asphalt, such as any of the polymer modifiedasphalts described above v. a shingle having the same reinforcementmaterial and a conventional oxidized asphalt have been demonstratedusing a modified version of the peel test prescribed by ASTM teststandard D1876. For example, referring to FIG. 15, a sample 1200 is cutfrom a shingle. The sample 1200 can be cut along the common bond area1202 of the shingle, with the reinforcement material 19 running throughthe center of the sample 1200. Approximately 1″ of the reinforcementmaterial 19 is pulled up and folded down at a 90 degree angle to thereinforcement material 19 remaining on the shingle as indicated by arrow1404. The reinforcement material 19 and the shingle material 1206 arepulled relatively apart in the cross-machine direction indicated byarrows 1404, 1410 to peel the reinforcement material 19 off of theshingle material 1206. For example, the reinforcement material 19 andthe shingle material 1206 can be pulled relatively apart in thecross-machine direction at a rate of 12″/min. The reinforcement material19 and the shingle material 1206 can be pulled apart for a total pulllength of 3.5″. In one exemplary embodiment, the average pull force iscomputed using the pull force data from a 1″ pull length mark to a 1.5″pull length mark. This area (between 1″ and 1.5″ of pull) is relativelysteady. For example, transverse adhesion values of a shingle having areinforcement material 19 and a polymer modified asphalt v. an otherwiseidentical shingle having the same reinforcement material and aconventional oxidized asphalt can be a greater than 5% increase in pullforce, a greater than 10% increase in pull force, a greater than 15%increase in pull force, or an at least about 19% increase in pull force.In one exemplary embodiment, the transverse adhesion of the improvedpolymer modified asphalt/reinforcement material shingle is greater than5 lbf, such as between 5 and 10 lbf, such as 6-9 lbf, such as 7.0-7.5lbf, such as about 7.3 lbf. In one exemplary embodiment, the enhancedtransverse adhesion described above is at room temperature (for both thePMA +Reinforcement shingle and the compared conventional asphalt plusreinforcement shingle), such as 73 degrees F. or about 73 degrees F.

Applicants have found that transverse adhesion can be an indicator ofenhanced cuttability. Increased transverse adhesion correlates toenhanced (easier/with less force exerted) cutting of the shingle throughthe area of the shingle with the reinforcement material 19.

Enhanced Cuttability for Polymer and Secondary Additive Modified AsphaltShingle having a Reinforcement Material

In one exemplary embodiment, the cuttability at elevated temperatures,such as 70 degrees C., of a shingle having a reinforcement material 19,such as any of the reinforcement materials described above, and apolymer modified asphalt, such as any of the polymer modified asphaltsdescribed above is enhanced compared the cuttability of an otherwiseidentical shingle made with a conventional oxidized asphalt (i.e. not apolymer modified asphalt). As used herein, the term “cuttability” refersto the force applied by a knife in the cross-machine direction (i.e. inthe direction perpendicular to the length of the reinforcement material)required to cut through the shingle material and reinforcement material.In this application, a lowering of the force needed to cut through theshingle material and the reinforcement material with the same cuttinginstrument is enhanced cuttability.

Improved cuttability of a shingle having a reinforcement material 19,such as any of the reinforcement materials described above, and apolymer modified asphalt, such as any of the polymer modified asphaltsdescribed above v. a shingle having the same reinforcement material anda conventional oxidized asphalt have been demonstrated using a test asdescribed below. For example, referring to FIGS. 16 and 17, a sample1200 is cut from a shingle. The sample 1200 can be cut along the commonbond area 1202 of the shingle, with the reinforcement material 19running through the center of the sample 1200. The sample is heated inan oven to 70 degrees C. to thoroughly heat the sample (e.g. 1 hour).Immediately after heating the sample, a hook razor blade 1500 (such as alarge hook razor blade, such as Stanley Part Number 11-983L) is orientedtransverse to the sample 1200 and is placed in engagement with thesample. The hook razor blade can be positioned on top of the granulesand the reinforcement material 19 as illustrated by FIG. 16. The hookrazor blade 1500 is pulled across the reinforcement material 19 and theshingle material 1206 to cut the sample in half. For example, the hookrazor blade 1500 can be pulled through the shingle at a rate of 20″/min.The average cutting force (i.e. pulling force applied between the hookrazor blade and the sample) needed to cut each of the samples of ashingle having a reinforcement material 19 and a polymer modifiedasphalt v. samples of an otherwise identical shingle having the samereinforcement material and a conventional oxidized asphalt can be atleast a 5% reduction in cutting force, at least a 10% reduction incutting force, at least a 15% reduction in cutting force, at least a 20%reduction in cutting force, at least a 25% reduction in cutting force,or an at least about 30% reduction in cutting force. In one exemplaryembodiment, the cutting force needed to cut the 70 degree C. sample ofthe improved polymer modified asphalt/reinforcement material shingle isless than 65 Newtons, such as between 20 and 65 Newtons, such as 30-55Newtons, such as 35-50 Newtons, such as 45-48 Newtons, such as about 47Newtons. In one exemplary embodiment, the cutting force needed to cutthe 70 degree C. sample of the polymer modified asphalt/reinforcementmaterial shingle is reduced as compared to an otherwise identicalshingle having the same reinforcement material and a conventionaloxidized asphalt is reduced by at least 5 Newtons, such as between 5 and35 Newtons, such as 10-30 Newtons, such as 15-25 Newtons, such as 18-22Newtons, such as about 20 Newtons.

Enhanced Cuttability for Polymer and Secondary Additive Modified AsphaltShingle having a Reinforcement Material

In one exemplary embodiment, the cuttability at room temperature, suchas 73 degrees F., of a shingle having a reinforcement material 19, suchas any of the reinforcement materials described above, and a polymermodified asphalt, such as any of the polymer modified asphalts describedabove is enhanced compared the cuttability of an otherwise identicalshingle made with a conventional oxidized asphalt (i.e. not a polymermodified asphalt).

Improved cuttability of a shingle having a reinforcement material 19,such as any of the reinforcements materials described above, and apolymer modified asphalt, such as any of the polymer modified asphaltsdescribed above v. a shingle having the same reinforcement material anda conventional oxidized asphalt have been demonstrated using a test asdescribed below. For example, referring to FIGS. 15 and 16, a sample1200 is cut from a shingle. The sample 1200 can be cut along the commonbond area 1202 of the shingle, with the reinforcement material 19running through the center of the sample 1200. The sample and ambienttemperature are room temperature, such as about 73 degrees F. A hookrazor blade 1500 (such as a large hook razor blade, such as Stanley PartNumber 11-983L) is oriented transverse to the sample 1200 and is placedin engagement with the sample. The hook razor blade can be positioned ontop of the granules and the reinforcement material 19 as illustrated byFIG. 16. The hook razor blade 1500 is pulled across the reinforcementmaterial 19 and the shingle material 1206 to cut the sample in half. Forexample, the hook razor blade 1500 can be pulled through the shingle ata rate of 20″/min. The average cutting force (i.e. pulling force appliedbetween the hook razor blade and the sample) needed to cut each of thesamples of a shingle having a reinforcement material 19 and a polymermodified asphalt v. samples of an otherwise identical shingle having thesame reinforcement material and a conventional oxidized asphalt can beat least a 5% reduction in cutting force, at least a 10% reduction incutting force, at least a 5% reduction in cutting force, at least a 7.5%reduction in cutting force, or an at least about 10% reduction incutting force. In one exemplary embodiment, the cutting force needed tocut the 73 degree F. sample of the improved polymer modifiedasphalt/reinforcement material shingle is less than 70 Newtons, such asbetween 20 and 70 Newtons, such as 40-65 Newtons, such as 45-60 Newtons,such as 55-59 Newtons, such as about 57.5 Newtons. In one exemplaryembodiment, the cutting force needed to cut the 73 degree F. sample ofthe polymer modified asphalt/reinforcement material shingle is reducedas compared to an otherwise identical shingle having the samereinforcement material and a conventional oxidized asphalt is reduced byat least 5 Newtons, such as between 5 and 12.5 Newtons, such as 6-10Newtons, such as 7-9 Newtons, such as about 7.5 Newtons.

Optional Treatment of the Reinforcement Material to Enhance Bondingbetween the Reinforcement Material and Polymer Modified Asphalt and/orbetween the Reinforcement Material and Sealant of an Overlying Shingle

In one exemplary embodiment, the reinforcement material is constructedto provide better adhesion of the reinforcement 19 to the polymermodified asphalt and/or better adhesion of the reinforcement 19 to thesealant or adhesive of an overlying shingle on the roof In someconfigurations, sealant is provided on the bottom surface of the tabs ofthe shingle at a lower end of the tabs as described above. When theshingles are installed on a roof, the sealant on the bottom surfaces ofthe tabs of an overlying course of shingles bonds with the reinforcement19 in the nail zone of an underlying course of shingles. This bondingconnects each overlying course of shingles to each underlying course ofshingles. The reinforcement 19 can be modified in a wide variety ofdifferent ways to enhance adhesion of the reinforcement 19 to thepolymer modified asphalt of the shingle and/or adhesion of thereinforcement 19 to the sealant. For example, the reinforcement 19 canbe modified by a surface treatment or chemistry that is pre-applied,post-applied or molecularly integrated to the reinforcement material. Inone exemplary embodiment, the reinforcement material 19 can be modifiedto enhance adhesion of the sealant to reinforcement material 19 in coldtemperatures, such as temperatures below 40 degrees F. The reinforcementmaterials 19 that are modified to enhance bonding of the reinforcementmaterial 19 to the polymer modified asphalt and/or enhance adhesion ofthe reinforcement 19 to the sealant or adhesive of an overlying shinglecan take a wide variety of different forms. For example, thereinforcement materials can be any of the reinforcement materials 19disclosed herein, including but not limited to woven or non-wovenpolyester tapes, and other woven and nonwoven polymer tapes.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt and/or better adhesion of the reinforcement 19to the sealant or adhesive of an overlying shingle on the roof is tointegrate an adhesion promoting chemical into the manufacturing processof the reinforcement material. The adhesion promoting chemical can takea wide variety of different forms and can be integrated into themanufacturing process of the reinforcing material in a wide variety ofdifferent ways. In one exemplary embodiment, the adhesion promotingchemical is an input material that is blended with other materials, suchas polyethylene or any of the other reinforcement materials disclosedherein, prior to extrusion of the reinforcement material. The adhesionpromoting chemical can be any material that enhances bonding between atape, such as a polyethylene or any of the other reinforcement materialsdisclosed herein, and polymer modified asphalt, such as any of thepolymer modified asphalts disclosed herein and/or a polymer modifiedasphalt sealant. For example, the reinforcement material can be a wovenor non-woven tape formed from strands, fibers, and/or tapes and theadhesion promoting chemical is blended with the material that forms thestrands, before the strands, fibers, and/or tapes are extruded.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt and/or better adhesion of the reinforcement 19to the sealant or adhesive of an overlying shingle on the roof is tocoat individual strands, fibers, and/or tapes of a woven or non-wovenreinforcement material with an adhesion promoting chemistry afterextrusion of the strands, fibers, and/or tapes. The adhesion promotingchemical can take a wide variety of different forms and can be appliedto strands, fibers, and/or tape(s) of the reinforcing material in a widevariety of different ways. The adhesion promoting chemical can be anymaterial that enhances bonding between a tape, such as a polyethylene orany of the other reinforcement materials disclosed herein, and polymermodified asphalt, such as any of the polymer modified asphalts disclosedherein and/or a polymer modified asphalt sealant.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt and/or better adhesion of the reinforcement 19to the sealant or adhesive of an overlying shingle on the roof is to addan adhesive promoting chemistry during the chemical, thermal, mechanicaland/or solvent bonding together of strands, fibers, and/or tapes of aareinforcement material 19. The adhesion promoting chemical can take awide variety of different forms and can be applied during bondingtogether of the strands, fibers, and/or tapes of the reinforcingmaterial in a wide variety of different ways. The adhesion promotingchemical can be any material that enhances bonding between a tape, suchas a polyethylene or any of the other reinforcement materials disclosedherein, and polymer modified asphalt, such as any of the polymermodified asphalts disclosed herein and/or a polymer modified asphaltsealant.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt and/or better adhesion of the reinforcement 19to the sealant or adhesive of an overlying shingle on the roof is to runfinished reinforcement material, such as a tape, through a secondary,adhesion enhancing process. The secondary, adhesion promoting processcan take a wide variety of different forms. For example, the side of afinished or previously manufactured tape that faces the polymer modifiedasphalt of the shingle, the side of the tape that faces the sealant ofan overlying shingle or both sides of the tape can be subjected to asecondary, adhesion promoting process. The secondary, adhesion promotingprocess can take a wide variety of different forms. The side of afinished or previously manufactured tape that faces the polymer modifiedasphalt of the shingle, the side of the tape that faces the sealant ofan overlying shingle or both sides can be sprayed, bathed, coronatreated, painted, powder coated, mercerizing, or other chemicalfinishing process with an adhesion promoting chemistry or secondarycoating material and/or roughened, perforated, or otherwise mechanicallyprocessed. In one exemplary embodiment, the side of the tape that facesthe polymer modified asphalt of the shingle is subjected to onesecondary, adhesion promoting process and the side of the tape thatfaces the sealant of an overlying shingle is subjected to anothersecondary, adhesion promoting process. In one exemplary embodiment, asecondary layer of material, such as a release tape, can be applied tothe surface of the tape. The secondary layer of material can be removedto expose the adhesive promoting layer or surface on the reinforcementmaterial during cold weather installations, such as installations thatare on days that are colder than 50 degrees F., such as days that arecolder than 40 degrees F.

One option for providing better adhesion of the reinforcement 19 to thesealant or adhesive of an overlying shingle on the roof is to spray orpaint a liquid or other phase material to the tape on the surface of thetape that faces the sealant of an overlying shingle in the field duringcold temperature installs, such as when outside temperatures are lessthan 40 degrees F. The sprayed or painted material can promote adhesionof the sealant to the tape in a variety of different ways. The sprayedor painted material can be a one part adhesive material or a two partadhesive material. A two part adhesive material can have a first partapplied to the tape and the other part applied to the sealant of theoverlying shingle.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt and/or better adhesion of the reinforcement 19to the sealant or adhesive of an overlying shingle on the roof is tomake the reinforcement material from a PET material and modify thesurfaces of the PET through NaOH modification. Increasing the surfaceroughness and the polarity of the surface through NaOH modification inturn increases adhesion due to an increase in carboxylic acid groups.

One option for providing better adhesion of the reinforcement 19 to thepolymer modified asphalt is to tailor the polymer modified asphaltcoating to increase the adhesion between reinforcement material and thepolymer modified asphalt shingle filled coating. The polymer modifiedasphalt coating can be formulated to achieve synergistic effects betweencoating performance and increased adhesion (rheological properties thatimprove both shingle aspects).

While various inventive aspects, concepts and features of the inventionsmay be described and illustrated herein as embodied in combination inthe exemplary embodiments, these various aspects, concepts and featuresmay be used in many alternative embodiments, either individually or invarious combinations and sub-combinations thereof. Unless expresslyexcluded herein all such combinations and sub-combinations are intendedto be within the scope of the present inventions.

Although several exemplary embodiments of the present invention havebeen described herein, it should be appreciated that many modificationscan be made without departing from the spirit and scope of the generalinventive concepts. All such modifications are intended to be includedwithin the scope of this invention and the related general inventiveconcepts.

1-103. (canceled)
 104. A roofing shingle comprising: a substrate; apolymer and secondary additive modified asphalt coating on thesubstrate; wherein the polymer and secondary additive modified asphaltcoating comprises: asphalt; a polymer additive; a secondary additive; astrip of nail zone reinforcement material on the polymer and secondaryadditive modified asphalt coating; and roofing granules on the polymerand secondary additive modified asphalt coating; wherein a longitudinaladhesion of the strip of nail zone reinforcing material to the polymerand secondary additive modified asphalt coating is greater than alongitudinal adhesion of an otherwise identical shingle having the samenail zone reinforcement material and a conventional oxidized asphaltwithout secondary additive and without polymer additive.
 105. Theroofing shingle of claim 104 wherein the secondary additive comprisesone or more of a wax, a salt of a fatty acid ester, and an amide of afatty acid.
 106. The roofing shingle of claim 104 wherein the secondaryadditive is an asphalt viscosity reducing agent.
 107. The roofingshingle of claim 104 wherein the longitudinal adhesion of the strip ofnail zone reinforcing material to the polymer and secondary additivemodified asphalt coating is more than 10% greater than the longitudinaladhesion of the otherwise identical shingle.
 108. The roofing shingle ofclaim 104 wherein the strip of nail zone reinforcement material is awoven polyester fabric.
 109. The roofing shingle of claim 104 whereinthe polymer and secondary additive modified asphalt coating furthercomprises a filler and wherein the polymer and secondary additivemodified asphalt coating comprises 85-99 wt. % asphalt, 1-13 wt. %polymer additive, and 1-6 wt. % secondary additive prior to addition ofthe filler.
 110. The roofing shingle of claim 104 wherein the polymeradditive is styrene-butadiene rubber.
 111. The roofing shingle of claim109 wherein the polymer additive is styrene-butadiene rubber.
 112. Theroofing shingle of claim 104 wherein the secondary additive is aFischer-Tropsch secondary additive.
 113. The roofing shingle of claim109 wherein the secondary additive is a Fischer-Tropsch wax.
 114. Theroofing shingle of claim 109 wherein the longitudinal adhesion of thestrip of nail zone reinforcing material to the polymer and secondaryadditive modified asphalt coating is more than 10% greater than thelongitudinal adhesion of the otherwise identical shingle.
 115. A roofingshingle comprising: a substrate; a polymer and secondary additivemodified asphalt coating on the substrate; wherein the polymer andsecondary additive modified asphalt coating comprises: asphalt; apolymer additive; a secondary additive; a strip of nail zonereinforcement material on the polymer and secondary additive modifiedasphalt coating; and roofing granules on the polymer and secondaryadditive modified asphalt coating; wherein a longitudinal adhesion ofthe strip of nail zone reinforcing material to the polymer and secondaryadditive modified asphalt coating is greater than 1.25 lbf.
 116. Theroofing shingle of claim 115 wherein the secondary additive comprisesone or more of a wax, a salt of a fatty acid ester, and an amide of afatty acid.
 117. The roofing shingle of claim 115 wherein the secondaryadditive is an asphalt viscosity reducing agent.
 118. The roofingshingle of claim 115 wherein the strip of nail zone reinforcementmaterial is a woven polyester fabric.
 119. The roofing shingle of claim115 wherein the polymer and secondary additive modified asphalt coatingfurther comprises a filler and wherein the polymer and secondaryadditive modified asphalt coating comprises 85-99 wt. % asphalt, 1-13wt. % polymer additive, and 1-6 wt. % secondary additive prior toaddition of the filler.
 120. The roofing shingle of claim 115 whereinthe polymer additive is styrene-butadiene rubber.
 121. The roofingshingle of claim 119 wherein the polymer additive is styrene-butadienerubber.
 122. The roofing shingle of claim 115 wherein the secondaryadditive is a Fischer-Tropsch wax.
 123. The roofing shingle of claim 119wherein the secondary additive is a Fischer-Tropsch wax.
 124. Theroofing shingle of claim 115 wherein the longitudinal adhesion of thestrip of nail zone reinforcing material to the polymer and secondaryadditive modified asphalt coating is more than 10% greater than thelongitudinal adhesion of an otherwise identical shingle.
 125. Theroofing shingle of claim 119 wherein the longitudinal adhesion of thestrip of nail zone reinforcing material to the polymer and secondaryadditive modified asphalt coating is more than 10% greater than thelongitudinal adhesion of an otherwise identical shingle. 126-202.(canceled)